Isocyanate production process using composition containing carbamic acid ester and aromatic hydroxy compound, and composition for transfer and storage of carbamic acid ester

ABSTRACT

An object of the present invention is to provide an isocyanate production process, which is free of the various problems found in the prior art, and which uses a composition containing a carbamic acid ester and an aromatic hydroxy compound when producing isocyanate without using phosgene, as well as a carbamic acid ester composition for transferring or storing carbamic acid ester. The present invention discloses an isocyanate production process including specific steps and using a composition containing a carbamic acid ester and an aromatic hydroxy compound, as well as a composition for transfer or storage of carbamic acid ester comprising the carbamic acid ester and the specific aromatic hydroxy compound.

TECHNICAL FIELD

The present invention relates to a process for producing an isocyanateusing a composition containing a carbamic acid ester and an aromatichydroxy compound. Moreover, the present invention relates to acomposition for transfer and storage of carbamic acid ester, containingsuch a composition.

BACKGROUND ART

Carbamic acid esters (urethanes) are compounds that are widely used inapplications such as polyurethane foam, surface coatings, elastomers,paints and adhesives, and are industrially extremely useful. Inaddition, carbamic acid esters are also useful as raw materials forproducing isocyanates without using phosgene.

Industrial production of isocyanates mainly uses a reaction between anamine compound and phosgene (“phosgene method”), and nearly the entireamount of isocyanates produced worldwide is produced using the phosgenemethod. However, the phosgene method has numerous problems.

Firstly, a large amount of phosgene is used as a raw material. Phosgeneis an extremely highly toxic substance, its handling requires specialprecautions to prevent handlers from being exposed, and special measuresare also required to detoxify waste.

Secondly, since a large amount of highly corrosive hydrogen chloride isproduced as a by-product of the phosgene method, in addition torequiring a process for detoxifying this hydrogen chloride, sincehydrolysable salts are frequently contained in the isocyanates produced,in the case of using isocyanates produced according to the phosgenemethod, there are cases in which they have a detrimental effect on theweather resistance and heat resistance of polyurethane products.

In consideration of these factors, there is a need for a process forproducing isocyanate compounds that does not use phosgene. One processthat has been proposed for the production of isocyanates without usingphosgene involves thermal decomposition of carbamic acid ester.Isocyanates and hydroxy compounds have long been known to be obtainedfrom thermal decomposition of carbamic acid esters (see, for example,Non-Patent Document 1: Berchte der Deutechen Chemischen Gesellschaft,Vol. 3, p. 653, 1870). The basis reaction thereof is indicated by thefollowing formula:

R(NHCOOR′)_(x)→R(NCO)_(x) +xR′OH  (1)

(wherein R represents an organic residue having a valence of x, R′represents a monovalent organic residue, and x represents an integer of1 or more).

In this manner, although carbamic acid esters are industrially usefulcompounds, since carbamic acid esters easily form hydrogen bonds betweenmolecules from ester groups forming the carbamic acid ester, theyfrequently have a high melting point. Typically, in the case of using asubstance industrially, operations such as those for transferring thatsubstance or storing that substance in a storage tank for a fixed periodof time are required. In the transfer of a carbamic acid ester having ahigh melting point, a solid carbamic acid ester, for example, is crushedor treated with a vehicle for processing into the pellets and the likeprior to transfer, or the carbamic acid ester is liquefied prior totransfer by heating to a temperature higher than the melting point ofthe carbamic acid ester. However, in the case of transferring the solidcarbamic ester that has been treated with the vehicle for processinginto the pellets, there is a need for a complex apparatus to ensurestable transfer of a fixed amount of carbamic acid ester or the need fora process for maintaining the form of the carbamic acid ester within acertain range in cases of the risk of clogging of the transfer line orfrequent fluctuations in the form of the carbamic acid ester. On theother hand, in the case of transferring carbamic acid ester in the formof a liquid by heating, it is necessary to heat to a temperature higherthan the melting point of the carbamic acid ester (for example, 200° C.)in consideration of preventing solidification during transfer. In thecase of holding a carbamic acid ester under such high temperatures,undesirable side reactions may occur that cause a decrease in the yieldof the carbamic acid ester. Examples of such side reactions may includethe reactions of the following formulas (2) and (3) that occur due toisocyanate formed by the occurrence of a thermal decomposition reactionof carbamic acid ester as shown in formula (1) above, and the thermaldenaturation reaction of carbamic acid ester as shown in the followingformula (4) (see Non-Patent Document 1 and Non-Patent Document 2).

(wherein each of R and R′ independently represents an organic group suchas a aliphatic group or alicyclic group).

These side reactions not only lead to a decrease in the yield ofcarbamic acid ester, but in the case of handling carbamic acid esters inparticular, there may also be precipitation of polymeric solidsresulting in clogging of transfer lines or accumulation in storagetanks.

Several methods have been proposed to solve these problems.

Patent Document 1 discloses a method for storing or transportingaromatic urethane (carbamic acid ester equivalent to the product of areaction between an aromatic isocyanate and a hydroxy compound) in thepresence of an organic solvent. Although this method is characterized bythe use of from 1 to 10 times the weight, based on the aromaticurethane, of an organic solvent that is inert with respect to theurethane and the isocyanate corresponding to that urethane, in thismethod, a decrease in the urethane cannot be inhibited, and a largeamount of substances having unknown structures are produced.

In addition, Patent Document 2 discloses a method for storing anaromatic urethane solution by using 1,4-dioxane as a solvent fordissolving the urethane. However, in this method, since an equivalentamount (for example, 20 times the weight) of 1,4-dioxane must be usedwith respect to the urethane, this method had the problem of resultingin a decrease in the storage efficiency of the urethane.

In this manner, methods used to transfer or store carbamic acid esterswithout causing denaturation thereof still have problems remaining.

On the other hand, various processes have been proposed thus far for theproduction of carbamic acid esters.

According to the description of Patent Document 3, an aliphaticdiurethane and/or alicyclic diurethane and/or aliphatic polyurethaneand/or alicyclic polyurethane are obtained by reacting an aliphaticprimary diamine and/or alicyclic primary diamine and/or aliphaticprimary polyamine and/or alicyclic primary polyamine withO-alkylcarbamate in the presence of an alcohol and in the presence orabsence of a catalyst at 160 to 300° C. at a ratio of amine NH₂group:carbamate:alcohol of 1:0.8 to 10:0.25 to 50, followed by removingthe ammonia formed as necessary.

In addition, according to Patent Document 4, an aryl diurethane and/oraryl polyurethane is produced by reacting an aromatic primary amineand/or aromatic primary polyamine with O-alkylcarbamate in the presenceor absence of a catalyst and in the presence or absence of urea andalcohol to form an aryl diurethane and/or aryl polyurethane followed byremoving the ammonia formed as necessary.

Other publications contain descriptions relating to partial substitutionof urea and/or diamine by a carbonyl-containing compound such asN-substituted carbamate and/or dialkyl carbonate, or mono-substitutedurea, di-substituted urea, mono-substituted polyurea or di-substitutedpolyurea (see Patent Document 5, Patent Document 6, Patent Document 7,Patent Document 8 and Patent Document 9). Patent Document 10 describes aprocess for producing aliphatic O-arylurethane by reacting a (cyclic)aliphatic polyamine with urea and an aromatic hydroxy compound.

In addition, according to Patent Document 11, a process is disclosed forproducing a carbamic acid ester from an amine compound and dimethylcarbonate. This process reacts an amine compound and dimethyl carbonatein the presence of Lewis acid catalyst, lead, titanium, zirconiumcatalyst or alkaline catalyst and the like.

In this manner, although various methods are known for producingcarbamic acid esters, at the time of using these carbamic acid ester, anoperation is required for recovering the carbamic acid ester from amixture containing the carbamic acid ester produced according to thesemethods. Several methods have been disclosed for recovering carbamicacid esters.

Patent Document 12 discloses a method distilling one or more types ofdiurethanes in the presence of a low boiling point alcohol having analkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon grouphaving 5 or 6 carbon atoms. However, this method also had the problem ofsolid substances remaining in the distillation apparatus.

In addition, Patent Document 13 describes a method for distillativeseparation of an unreacted amine compound and alcohol from a reactionliquid obtained by reacting a carbonic acid ester and an amine compound.However, since a solution mainly containing carbamic acid ester isheated in the bottom of a distillation column during the time thedistillative separation operation is being carried out, a thermaldenaturation reaction like that described above may occur according tothis method as well, thereby preventing the obtaining of an adequaterecovery rate. In addition, Patent Document 14 describes a process forproducing isocyanate by thermal decomposition of a carbamic acid esterafter having synthesized the carbamic acid ester by reacting a diamineand dimethyl carbonate. In this process, although the carbamic acidester is isolated by distillative purification, this distillativepurification is preferably carried out in the presence of an inertsolvent having a boiling point at least 10° C. lower than the carbamicacid ester. In this distillative purification method, since the carbamicacid ester is heated in the bottom of a distillation column in the samemanner as the previously described method, the recovery rate cannot besaid to be adequate.

In this manner, methods for separating carbamic acid esters from amixture obtained in a carbamic acid ester production process still haveproblems remaining.

On the other hand, various methods have been proposed for producingisocyanates by using a carbamic acid ester as a raw material.

According to the description of Patent Document 3, an aliphaticdiurethane and/or alicyclic diurethane and/or aliphatic polyurethaneand/or alicyclic polyurethane are obtained by reacting an aliphaticprimary diamine and/or alicyclic primary diamine and/or aliphaticprimary polyamine and/or alicyclic primary polyamine withO-alkylcarbamate in the presence of an alcohol and in the presence orabsence of a catalyst at from 160 to 300° C. at a ratio of amine NH₂group:carbamate:alcohol of 1:0.8 to 10:0.25 to 50, followed by removingthe ammonia formed as necessary. The resulting diurethane and/orpolyurethane can be converted to the corresponding diisocyanate and/orhighly functional polyisocyanate as necessary. Detailed reactionconditions with respect to thermal decomposition are not described inthis publication.

According to Patent Document 4, an aromatic diisocyanate and/orpolyisocyanate are produced by going through the following two steps. Inthe first step, an aromatic primary amine and/or aromatic primarypolyamine are reacted with O-alkylcarbamate in the presence or absenceof a catalyst and in the presence or absence of urea and alcohol to forman aryl diurethane and/or aryl polyurethane followed by removing theammonia formed as necessary. In the second step, an aromatic isocyanateand/or aromatic polyisocyanate are obtained by thermal decomposition ofthe aryl diurethane and/or aryl polyurethane.

Several methods are known for forming a corresponding isocyanate andalcohol by thermal decomposition of a (cyclic) aliphatic, andparticularly aromatic monourethane and diurethane, and although thesemethods may include methods carried out in a gaseous phase at a hightemperature and methods carried out in a liquid phase undercomparatively low temperature conditions, since there are cases in whichthe reaction mixture forms precipitates, polymeric substances andocclusions in the reaction vessel and recovery apparatus due to theoccurrence of side reactions as described above, for example, economicefficiency is poor in the case of producing isocyanates over a longperiod of time.

Thus, chemical methods such as the use of a special catalyst (see PatentDocument 15 and Patent Document 16) or a catalyst in combination with aninert solvent (see Patent Document 17) have been disclosed to improveyield during thermal decomposition of urethanes.

More specifically, Patent Document 18 describes a process for producinghexamethylene diisocyanate comprising thermal decomposition ofhexamethylene diethylurethane in the presence of dibenzyl toluene usedas a solvent, and in the presence of a catalyst mixture containingmethyl toluenesulfonate and diphenyl tin dichloride. However, sincethere is no detailed description provided regarding production of thestarting components or isolation, purification or voluntary recovery ofthe solvent and catalyst mixture, it is not possible to assess theeconomic efficiency of this process.

According to the method described in Patent Document 19, urethane can beeasily decomposed to an isocyanate and an alcohol in a carbon-containingfluidized bed without using a catalyst. In addition, according to PatentDocument 20, hexamethylene dialkyl urethane can be decomposed in agaseous phase at a temperature in excess of 300° C. in the presence orabsence of a gas-permeable packaging material composed of, for example,carbon, copper, bronze, steel, zinc, aluminum, titanium, chromium,cobalt or quartz to form hexamethylene diisocyanate. According to thedescription of Patent Document 14, the process is carried out in thepresence of a hydrogen halide and/or hydrogen halide donor. However,this method is unable to achieve a hexamethylene diisocyanate yield of90% or more. This is because the decomposition products are partiallyrebonded resulting in the formation of urethane bonds. Thus, furtherpurification of hexamethylene diisocyanate by distillation is required,and this frequently results in an increase in yield loss.

Moreover, Patent Document 21 discloses that a monocarbamate can bedecomposed at a satisfactory yield without using a solvent in thepresence or absence of a catalyst and/or stabilizer advantageously underreduced pressure and at a comparatively low temperature. Thedecomposition products (monoisocyanate and alcohol) are removed from theboiling reaction mixture by distillation and are captured separately byfractional condensation. A method is described in a generic form forpartially removing the reaction mixture in order to remove by-productsformed during thermal decomposition. Thus, although by-products can beremoved from the bottom of the reaction vessel, the problem with respectto the case of adhering to the walls of the reaction vessel aspreviously described remains, and the problem with respect to long-termoperation is unresolved. In addition, there is no description regardingthe industrial use of the removed residue (containing a large amount ofuseful components).

According to the description of Patent Document 22, thermaldecomposition of an aliphatic, alicyclic or aromatic polycarbamate iscarried at from 150 to 350° C. and from 0.001 to 20 bar in the presenceof an inert solvent and in the presence or absence of a catalyst,auxiliary agent in the form of hydrogen chloride, organic acid chloride,alkylating agent or organic tin chloride. By-products formed can beremoved continuously from the reaction vessel together with the reactionsolution, for example, and a corresponding amount of fresh solvent orrecovered solvent is added simultaneously. A disadvantage of this methodis that, for example, a decrease in the space-time yield ofpolyisocyanate occurs due to the use of a refluxing solvent, and what ismore, a large amount of energy is required, including that forrecovering the solvent, for example. Moreover, the auxiliary agent thatis used is volatile under the reaction conditions, and the decompositionproducts may be contaminated. In addition, the amount of residue islarge relative to the amount of polyisocyanate formed, thereby makingthe economic efficiency and reliability as an industrial method suspect.

Patent Document 23 describes one method for continuous thermaldecomposition of a carbamate, such as an alicyclic diurethane5-(ethoxycarbonylamino)-1-(ethoxycarbonylaminomethyl)-1,3,3-trimethylcyclohexane,supplied along the inner surface of a tubular reaction vessel in aliquid form in the presence of a high boiling point solvent. This methodhas the disadvantages of low yield and low selectivity during productionof a (cyclic) aliphatic diisocyanate. In addition, there is nodescription of a continuous method accompanying recovery of rebonded orpartially decomposed carbamate, and post-treatment of solvent containingby-products and catalyst is also not mentioned.

The description of Patent Document 24 relates to a circulation methodfor producing (cyclic) aliphatic diisocyanate by converting acorresponding diamine to diurethane followed by thermal decomposition ofthis urethane. This method minimizes the decrease in yield byrecirculating the product from a urethane decomposition step to anurethanation step following reaction with alcohol. By-products that areunable to be recirculated are removed by separation by distilling amixture of urethanation products, and in this case, unwanted residueforms in the form of bottom products while all comparatively low boilingpoint components, including diurethane, are removed from the top of thecolumn. This method, however has a disadvantage of using a large amountof energy. This is because all diurethane is required to be evaporatedin the presence of a catalyst, and this diurethane must be evaporated ata temperature level within the range of the decomposition temperature ofurethane. Isocyanate groups formed in useful products react withresidual urethane groups, frequently resulting in the formation ofcomparatively high molecular weight by-products that cause a reductionin yield.

In addition, according to the description of Patent Document 25, amethod is disclosed whereby unwanted by-products are partially removedprior to carrying out thermal decomposition of polyurethane. Thedisadvantage of this method is that the yield of isocyanate decreases asa result of polyurethane being contained in the partially removedby-products. In addition, since polymeric compounds form and adhere tothe reaction vessel as a result of heating of by-products remaining inthe reaction vessel without being discharged from the reaction vessel,long-term, continuous operation is difficult.

As has been described above, processes for producing isocyanates usingcarbamic acid esters as raw materials have numerous problems to besolved and have yet to be industrialized.

Patent Document 1: Japanese Patent Application Laid-open No. S59-48452

Patent Document 2: Japanese Patent Application Laid-open No. 2004-262831

Patent Document 3: U.S. Pat. No. 4,497,963

Patent Document 4: U.S. Pat. No. 4,290,970

Patent Document 5: U.S. Pat. No. 4,388,238)

Patent Document 6: U.S. Pat. No. 4,430,505)

Patent Document 7: U.S. Pat. No. 4,480,110

Patent Document 8: U.S. Pat. No. 4,596,678

Patent Document 9: U.S. Pat. No. 4,596,679

Patent Document 10: European Patent Laid-open No. 0320235

Patent Document 11: U.S. Pat. No. 4,395,565

Patent Document 12: Japanese Patent Application Laid-open No. H10-87598

Patent Document 13: Japanese Patent Application Laid-open No. 2001-48839

Patent Document 14: Japanese Patent Application Laid-open No. S64-85956

Patent Document 15: U.S. Pat. No. 2,692,275

Patent Document 16: U.S. Pat. No. 3,734,941

Patent Document 17: U.S. Pat. No. 4,081,472

Patent Document 18: U.S. Pat. No. 4,388,426

Patent Document 19: U.S. Pat. No. 4,482,499

Patent Document 20: U.S. Pat. No. 4,613,466

Patent Document 21: U.S. Pat. No. 4,386,033

Patent Document 22: U.S. Pat. No. 4,388,246

Patent Document 23: U.S. Pat. No. 4,692,550

Patent Document 24: European Patent No. 0355443

Patent Document 25: Japanese Patent No. 3382289

Non-Patent Document 1: Berchte der Deutechen Chemischen Gesellschaft,Vol. 3, p. 653, 1870

Non-Patent Document 2: Journal of American Chemical Society, Vol. 81, p.2138, 1959

DISCLOSURE OF INVENTION Problems to be Solved by the Invention

An object of the present invention is to provide an isocyanateproduction process, which is free of the various problems found in theprior art, that uses a composition containing a carbamic acid ester andan aromatic hydroxy compound, and a carbamic acid ester composition fortransferring or storing carbamic acid ester.

Means for Solving the Problems

Therefore, as a result of conducting extensive studies on theabove-mentioned problems, the inventors of the present invention foundthat isocyanate can be produced in good yield by an isocyanateproduction process containing specific steps that uses a compositioncontaining a carbamic acid ester and a specific aromatic hydroxycompound, thereby leading to completion of the present invention. Inaddition, the inventors of the present invention also found that thecarbamic acid ester composition containing the carbamic acid ester andthe specific aromatic hydroxy compound is preferable as a compositionfor transferring or storing carbamic acid ester, thereby leading tocompletion of the present invention.

Namely, according to the first aspect of the present invention, thereare provided:

[1] a process for producing an isocyanate using a composition containinga carbamic acid ester and an aromatic hydroxy compound, the processcomprising the step of transferring the composition to a reaction vesselin which a thermal decomposition reaction of the carbamic acid esteroccurs,

wherein when number of mole of an ester group constituting the carbamicacid ester is defined as A, and number of mole of the aromatic hydroxycompound is defined as B, then a ratio of B to A is within a range offrom 0.1 to 50,

a melting point of the carbamic acid ester is 200° C. or lower, and

a melting point of the aromatic hydroxy compound is 190° C. or lower,

[2] the process according to item [1], wherein isocyanate is produced bya process comprising the following steps (1), (3), (4) and (5), or aprocess comprising the following steps (2), (3), (4) and (5):

step (1): reacting an amine compound and the carbonic acid ester so asto obtain a mixture containing a carbamic acid ester, an alcohol and acarbonic acid ester;

step (2): reacting an amine compound, an urea and an alcohol so as toobtain a mixture containing a carbamic acid ester, an alcohol and a ureacompound;

step (3): separating the alcohol and the carbonic acid ester or the ureacontained in the mixture by using the mixture of step (1) or step (2)and the aromatic hydroxy compound so as to obtain a compositioncontaining the carbamic acid ester and the aromatic hydroxy compound;

step (4): transferring the composition obtained in step (3) in a liquidstate to a reaction vessel in which step (5) is carried out; and

step (5): producing the isocyanate using the composition transferred instep (4),

[3] the process according to item [2], wherein a normal boiling point ofthe aromatic hydroxy compound is higher than a normal boiling point of acompound represented by ROH having a structure in which a hydrogen atomis added to RO constituting the ester group of the carbamic acid ester(wherein R represents an alkyl group and O represents an oxygen atom),[4] the process according to item [3], wherein a normal boiling point ofthe aromatic hydroxy compound is higher than a normal boiling point of acompound represented by ROCOOR having a structure in which an RO groupconstituting the ester group of the carbamic acid ester (wherein Rrepresents an alkyl group and O represents an oxygen atom) is bondedthrough a carbonyl group,[5] the process according to item [4], wherein the step (3) is a step inwhich the composition containing the carbamic acid ester and thearomatic hydroxy compound is obtained from a mixture of the mixture ofthe step (1) or the step (2) and the aromatic hydroxy compound byseparating the alcohol and the carbonic acid ester or the urea,[6] the process according to item [5], wherein the step (3) is a stepcarried out in a distillation column, in which the compositioncontaining the carbamic acid ester and the aromatic hydroxy compound isobtained from a bottom of the distillation column by supplying themixture of the step (1) or the step (2) to the distillation column in aform of a mixture with the aromatic hydroxy compound, and recovering thealcohol and the carbonic acid ester or the urea from a top of thecolumn,[7] the process according to item [4], wherein the step (3) is a step inwhich a mixture obtained by separating all or a portion of the alcoholand/or a portion of the carbonic acid ester or the urea from the mixtureof the step (1) or the step (2) is mixed with the aromatic hydroxycompound to obtain a mixture, and the carbonic acid ester or the urea isseparated from the mixture,[8] the process according to item [7], wherein the step (3) is a stepcarried out in a distillation column, and further comprises thefollowing steps (3-1) and (3-2):

step (3-1): supplying the mixture of the step (1) or the step (2) to thedistillation column, an alcohol and/or a carbonic acid ester or an ureabeing recovered from a top of the column, and a mixture containing thecarbamic acid ester, the alcohol and/or the carbonic acid ester or theurea being recovered from a bottom of the column; and

step (3-2): supplying the mixture of the step (3-1) to the distillationcolumn in a form of a mixture with the aromatic hydroxy compound, thealcohol and/or the carbonic acid ester or the urea being recovered fromthe top of the column, and the composition containing the carbamic acidester and the aromatic hydroxy compound being recovered from the bottomof the column,

[9] the process according to item [2], further comprising a step inwhich the carbonic acid ester or the urea separated in the step (3) isreused as the carbonic acid ester of the step (1) or the urea of thestep (2),[10] the process according to item [2], wherein the step (4) is carriedout at 180° C. or lower,[11] the process according to item [2], wherein the step (5) is a stepin which the carbamic acid ester contained in the composition of thestep (4) is subjected to a thermal decomposition reaction, and in whicha low boiling point component formed by the thermal decompositionreaction is recovered as a gaseous component from the reaction vessel inwhich the thermal decomposition reaction occurs, and all or a portion ofthe mixture containing the carbamic acid ester and/or the aromatichydroxy compound is recovered from the bottom of the reaction vessel,[12] the process according to item [11], wherein the low boiling pointcomponent is an alcohol derived from the carbamic acid ester,[13] the process according to item [2], wherein the step (5) is a stepin which the composition of the step (4) is heated, the carbamic acidester and the aromatic hydroxy compound which are contained in thecomposition are reacted to obtain an aryl carbamate having a groupderived from the aromatic hydroxy compound, and the aryl carbamate issubjected to a thermal decomposition reaction so as to produce anisocyanate,[14] the process according to item [13], wherein the step (5) comprisesthe following step (5-1) and step (5-2):

step (5-1): reacting the carbamic acid ester and aromatic hydroxycompound which are contained in the composition of the step (4), a lowboiling point component formed being recovered in a form of a gaseouscomponent, and a reaction liquid containing the aryl carbamate and thearomatic hydroxy compound being removed from the bottom of the reactionvessel in which the reaction occurs; and

step (5-2): supplying the reaction liquid of the step (5-1) to areaction vessel in which a thermal decomposition reaction occurs, thearyl carbamate being subjected to a thermal decomposition reaction, atleast one of either an isocyanate or an aromatic hydroxy compound whichare formed being recovered in a form of a gaseous component, and all ora portion of a mixture containing the isocyanate and/or the aromatichydroxy compound and/or the aryl carbamate not recovered in a form of agaseous component being recovered from the bottom of the reactionvessel,

[15] the process according to item [14], wherein the low boiling pointcomponent of the step (5-1) is an alcohol derived from the carbamic acidester,[16] the process according to item [11] or [14], wherein the aromatichydroxy compound is recovered from the mixture according to item [11]recovered from the bottom of the reaction vessel and containing thecarbamic acid ester and/or the aromatic hydroxy compound, or thereaction liquid of the step (5-1) according to item [14], the mixturerecovered from the bottom of the reaction vessel and/or the compoundrecovered in the form of a gaseous component in step the (5-2) accordingto item [14], and the aromatic hydroxy compound is reused as thearomatic hydroxy compound of the step (3),[17] the process according to item [2], wherein the alcohol separated inthe step (3) according to item [2] and/or the alcohol according to item[10] and/or item [13], is used as all or a portion of the alcohol in thestep (2) according to item [2],[18] the process according to item [4], wherein a molecular weight ofthe aromatic hydroxy compound is within a range of from 120 to 370,[19] the process according to item [18], wherein the aromatic hydroxycompound is a compound having one hydroxyl group directly bonded to anaromatic hydrocarbon ring constituting the aromatic hydroxy compound,[20] the process according to item [19], wherein the aromatic hydroxycompound is an aromatic hydroxy compound which is represented by thefollowing formula (5), and which has at least one substituent R¹:

(wherein ring A represents a single or multiple aromatic hydrocarbonring which may have a substituent, and which have 6 to 20 carbon atoms,and

R¹ represents an aliphatic group having 1 to 20 carbon atoms, analiphatic alkoxy group having 1 to 20 carbon atoms, an aryl group having6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, anaralkyl group having 7 to 20 carbon atoms or an aralkyloxy group having7 to 20 carbon atoms, the above groups containing an atom selected fromthe group consisting of carbon, oxygen and nitrogen atoms, and R¹ maybond with A to form a ring structure),

[21] the process according to item [20], wherein the aromatic hydroxycompound has a structure in which ring A contains at least one structureselected from the group consisting of a benzene ring, a naphthalene ringand an anthracene ring,[22] the process according to item [21], wherein the aromatic hydroxycompound is a compound represented by the following formula (6):

(wherein, each of R², R³, R⁴, R⁵ and R⁶ independently represents ahydrogen atom, or an aliphatic group having 1 to 20 carbon atoms, analiphatic alkoxy group having 1 to 20 carbon atoms, an aryl group having6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, anaralkyl group having 7 to 20 carbon atoms or an aralkyloxy group having7 to 20 carbon atoms, the above groups containing an atom selected fromthe group consisting of carbon, oxygen and nitrogen atoms, and at leastone of R², R³, R⁴, R⁵ and R⁶ is not a hydrogen atom),[23] the process according to item [22], wherein the aromatic hydroxycompound is a compound represented by the formula (2) in which R² is nota hydrogen atom,[24] the process according to item [23], wherein the aromatic hydroxycompound is a compound represented by the formula (2) in which a totalnumber of carbon atoms constituting R² and R⁶ is from 2 to 20,[25] the process according to item [2], wherein the amine compound ofthe step (1) is a polyamine compound,[26] the process according to item [25], wherein the amine compound is acompound represented by the following formula (7):

(wherein R⁷ represents a group which is selected from the groupconsisting of an aliphatic group having 1 to 20 carbon atoms and anaromatic group having 6 to 20 carbon atoms, the aliphatic group and thearomatic group contain an atom selected from carbon and oxygen atoms,and have a valence equal to n, and

n represents an integer of 2 to 10),

[27] the process according to item [26], wherein the polyamine compoundis a diamine compound in which n in the formula (3) is 2,[28] the process according to item [27], wherein the diamine compound isa compound in which R⁷ in the formula (3) is an aliphatic group whichhas 1 to 20 carbon atoms, and which contains an atoms selected fromcarbon and oxygen atoms,[29] the process according to item [28], wherein the diamine compound isat least one compound selected from the group consisting of compoundsrepresented by the following formulas (8), (9) and (10):

[30] the process according to item [2], wherein the carbonic acid esteris a compound represented by the following formula (11):

(wherein R⁸ represents a linear or branched alkyl group having 1 to 8carbon atoms),[31] the process according to item [30], wherein the carbonic acid esteris produced by a process comprising the following step (A) and step (B):

step (A): reacting an organic tin compound having a tin-oxygen-carbonbond and carbon dioxide so as to obtain a reaction mixture containingthe carbonic acid ester; and

step (B): separating the carbonic acid ester from the reaction mixtureas well as obtaining a distillation residue,

[32] the process according to item [31], further comprising thefollowing step (C) and step (D) in addition to the step (A) and the step(B) according to item [31]:

step (C): reacting the distillation residue obtained in step (B) withalcohol so as to form an organic tin compound having a tin-oxygen-carbonbond and a water, followed by removing the water from a reaction system;and

step (D): reusing the organic tin compound having the tin-oxygen-carbonbond obtained in the step (C) as the organic tin compound having atin-oxygen-carbon bond of step (A),

[33] the process according to item [32], wherein the alcohol separatedin the step (3) according to item [2] and/or the alcohol according toitem [10] and/or item [13]is used as all or a portion of the alcohol inthe step (C) according to item [32],[34] the process according to item [2], wherein the alcohol of the step(1) is an alcohol having an alkyl group derived from the carbonic acidester,[35] the process according to item [2], wherein the reaction between theamine compound and the carbonic acid ester in the step (1) is carriedout in the presence of a metal alkoxide compound,[36] the process according to item [35], wherein the metal alkoxidecompound is an alkoxide compound of an alkaline metal or an alkalineearth metal,[37] the process according to item [36], wherein an alkyl groupconstituting the carbonic acid ester is identical to an alkyl groupconstituting the metal alkoxide compound,[38] the process according to item [2], wherein the alcohol of the step(2) is a compound represented by the following formula (12):

R⁹—OH  (12)

(wherein R⁹ represents a linear or branched alkyl group having 1 to 10carbon atoms),[39] the process according to item [2], wherein the carbamic acid esteris a polycarbamic acid ester,[40] the process according to item [39], wherein the polycarbamic acidester is a compound represented by the following formula (13):

(wherein R⁷ has the same meaning as defined above,

R¹¹ represents an aliphatic group or an aromatic group which has 1 to 10carbon atoms, and which contains an atom selected from carbon and oxygenatoms, and

n represents an integer of 2 to 10),

[41] the process according to item [40], wherein the polycarbamic acidester is a compound represented by the formula (9) in which n is 2,[42] the process according to item [41], wherein the polycarbamic acidester is a compound represented by the formula (9) in which R¹¹ is analiphatic group which has 1 to 10 carbon atoms, and which contains anatom selected from carbon and oxygen atoms,[43] the process according to item [42], wherein the polycarbamic acidester is a compound represented by the formula (9) in which R⁷ is agroup selected from the group consisting of an alkyl group having 1 to20 carbon atoms and a cycloalkyl group having 5 to 20 carbon atoms,[44] the process according to item [43], wherein the polycarbamic acidester is at least one of compound selected from the group consisting ofcompounds represented by the following formulas (14), (15) and (16):

(wherein R¹¹ has the same meaning as defined above).

In addition, according to the second aspect of the present invention,there is provides:

[45] a composition for transfer and storage of a carbamic acid estercomprising: a carbamic acid ester; and an aromatic hydroxy compound,wherein

when number of mole of an ester group constituting the carbamic acidester is defined as A, and number of mole of an aromatic hydroxycompound is defined as B, then a ratio of B to A is within a range offrom 0.1 to 50,

a melting point of the carbamic acid ester is 200° C. or lower, and

a melting point of the aromatic hydroxy compound is 190° C. or lower.

Advantageous Effects of the Invention

Use of the composition according to the present invention enablesisocyanate to be efficiently produced without using phosgene. Inaddition, the composition according to the present invention is able toinhibit a thermal decomposition reaction of carbamic acid ester duringtransfer and storage thereof.

BEST MODE FOR CARRYING OUT THE INVENTION

The following provides a detailed explanation of the best mode forcarrying out the present invention (to be referred to as the “presentembodiment”). Furthermore, the present invention is not limited to thefollowing present embodiment, but rather can be modified in various wayswithin the scope of the gist thereof.

An explanation is first provided of a composition comprising a carbamicacid ester and an aromatic hydroxy compound in the present embodiment.

In the composition comprising the carbamic acid ester and the aromatichydroxy compound in the present embodiment:

when the number of mole of an ester group constituting the carbamic acidester contained in the composition is defined as A, and the number ofmole of the aromatic hydroxy compound contained in the composition isdefined as B, then a ratio of B to A (B/A) is preferably within a rangeof from 0.1 to 50, and a melting point of the composition is 150° C. orlower. In a preferable aspect of the present embodiment, the compositionis a composition for transfer and storage of carbamic acid ester.

Since carbamic acid esters used in the present embodiment easily formhydrogen bonds between molecules by the ester groups constituting thecarbamic acid esters, they frequently have a high melting point. In thetransfer of such a carbamic acid ester, a solid carbamic acid ester, forexample, is crushed or treated with a vehicle for processing intopellets and the like prior to transfer, or the carbamic acid ester isliquefied prior to transfer by heating to a temperature higher than themelting point of the carbamic acid ester. However, in the case oftransferring the solid carbamic ester that has been treated with thevehicle, there is a need for a complex apparatus to ensure stabletransfer of a fixed amount of carbamic acid ester or the need for aprocess for maintaining the form of the carbamic acid ester within acertain range in cases of the risk of clogging of the transfer line orfrequent fluctuations in the form of the carbamic acid ester. On theother hand, in the case of transferring carbamic acid ester in the formof a liquid by heating, although it is necessary to heat to atemperature higher than the melting point of the carbamic acid ester(for example, 200° C.) in consideration of preventing solidificationduring transfer, in the case of holding a carbamic acid ester under suchhigh temperatures, there are frequently cases in which isocyanate may beformed at undesirable locations due to the occurrence of a thermaldecomposition reaction of the carbamic acid ester or the occurrence of athermal denaturation reaction of the carbamic acid ester as previouslydescribed. The composition of the present embodiment demonstrates theeffect of being able to maintain the stability of the carbamic acidester by inhibiting thermal denaturation of the carbamic acid ester inthe composition during transfer or storage of the composition. Althoughthe mechanism by which the effect of inhibiting thermal denaturation ofthe carbamic acid ester is demonstrated is not clear, the inventors ofthe present invention presumed that, as a result of the aromatic hydroxycompound that forms the composition forming hydrogen bonds betweenurethane bonds (—NHCOO—) of the carbamic acid ester and the aromatichydroxy compound, a state is formed in which the urethane bonds havedifficulty in approaching each other, thereby making it difficult for areaction that forms urea bonds to occur as in, for example, a reactionthat forms urea bonds represented by formula (2) above.

In the composition of the present embodiment, although the number ofmole (B) of the aromatic hydroxy compound is preferably greater than thenumber of mole (A) of the ester group constituting the carbamic acidester, on the other hand, in consideration of carbamic acid estertransfer efficiency and the size of the storage tank at the time ofstorage, the ratio of B to A (B/A) is preferably from 0.2 to 30, morepreferably from 0.3 to 20 and even more preferably from 0.5 to 10.

In addition, the melting point of the carbamic acid ester constitutingthe composition of the present embodiment is 200° C. or lower, themelting point of the aromatic hydroxy compound is preferably 190° C. orlower, and the composition composed of the carbamic acid ester and thearomatic hydroxy compound is preferably a homogeneous liquid at 180° C.When transferring the composition in liquid form, although thecomposition is made to be in a liquid form by heating the composition toa temperature equal to or higher than the melting point thereof, in thecase the temperature at which the composition becomes a homogeneousliquid is higher than 180° C., thermal decomposition of the carbamicacid ester constituting the composition occurs when transforming thecomposition into liquid form, thereby resulting in the case ofisocyanate being formed at undesirable locations and making thisundesirable. From such a viewpoint, the temperature at which thecomposition becomes a homogeneous liquid is preferably 180° C. or lower,and in consideration of the ease of maintaining the temperature of thetransfer line and the like, the temperature is more preferably 150° C.or lower and even more preferably 100° C. or lower.

In general, the term “melting point” refers to a temperature when asolid phase and liquid phase are considered to be in a state ofequilibrium, and indicates a value based on a pressure of oneatmosphere. In the present embodiment, the melting point can be measuredby the known method, such as with a melting point measuring apparatusdescribed in the literature (Combined Chemical Dictionary 9, p. 357,Kyoritsu Shuppan Co., Ltd., Japan, 2003). In addition, melting point canreadily be measured by differential scanning calorimetry (DSC) ordifferential thermal analysis (DTA), and for example, the endothermicpeak measured during heating of a solid substance at a heating rate of5° C./min under a nitrogen atmosphere with a differential scanningcalorimeter can be defined as the melting point.

<Carbamic Acid Ester>

There are no particular limitations on the carbamic acid ester used inthe present embodiment, and polycarbamic acid esters are usedpreferably. Examples of polycarbamic acid esters may include compoundsrepresented by the following formula (17):

(wherein R⁷ represents a group selected from the group consisting of analiphatic group having 1 to 20 carbon atoms and an aromatic group having6 to 20 carbon atoms, the above groups containing an atom selected fromcarbon and oxygen atoms, and having a valence equal to n,

R¹¹ represents an aliphatic group or aromatic group having 1 to 10carbon atoms which contains an atom selected from carbon and oxygenatoms, and

n represents an integer of 2 to 10).

In formula (17) above, n is preferably a number selected from integersof 2 or more, and more preferably polycarbamic acid esters in which n is2.

R¹¹ in the formula (17) preferably represents an aliphatic group having1 to 10 carbon atoms containing an atom selected from carbon and oxygenatoms, and more preferably a hydrocarbon group having 1 to 10 carbonatoms. Examples of such R¹¹ may include alkyl groups in which the numberof carbon atoms constituting the group is a number selected fromintegers of 1 to 10, such as a methyl group, an ethyl group, a propylgroup (including isomers), a butyl group (including isomers), a pentylgroup (including isomers), a hexyl group (including isomers), a heptylgroup (including isomers) or an octyl group (including isomers); andcycloalkyl groups in which the number of carbon atoms constituting thegroup is a number selected from integers of 5 to 10, such as acyclopentyl group, a cyclohexyl group, a cycloheptyl group or acyclooctyl group.

R⁷ in the formula (17) more preferably represents an alkyl group having1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms,and examples of such R⁷ may include linear hydrocarbon groups such asmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene,hexamethylene or octamethylene; unsubstituted alicyclic hydrocarbongroups such as cyclopentane, cyclohexane, cycloheptane, cyclooctane orbis(cyclohexyl)alkane; alkyl-substituted cyclohexanes such asmethylcyclopentane, ethylcyclopentane, methylcyclohexane (includingisomers), ethylcyclohexane (including isomers), propylcyclohexane(including isomers), butylcyclohexane (including isomers),pentylcyclohexane (including isomers) or hexylcyclohexane (includingisomers); dialkyl-substituted cyclohexanes such as dimethylcyclohexane(including isomers), diethylcyclohexane (including isomers) ordibutylcyclohexane (including isomers); trialkyl-substitutedcyclohexanes such as 1,5,5-trimethylcyclohexane,1,5,5-triethylcyclohexane, 1,5,5-tripropylcyclohexane (includingisomers) or 1,5,5-tributylcyclohexane (including isomers);monoalkyl-substituted benzenes such as toluene, ethylbenzene orpropylbenzene; dialkyl-substituted benzenes such as xylene,diethylbenzene or dipropylbenzene; and aromatic hydrocarbons such asdiphenylalkane or benzene. In particular, hexamethylene, phenylene,diphenylmethane, toluene, cyclohexane, xylenyl, methylcyclohexane,isophorone and dicyclohexylmethane are used preferably.

Examples of carbamic acid esters represented by the formula (17) mayinclude alkyl carbamates such as N,N′-hexanediyl-bis-carbamic aciddimethyl ester, N,N′-hexanediyl-bis-carbamic acid diethyl ester,N,N′-hexanediyl-bis-carbamic acid dibutyl ester (including isomers),N,N′-hexanediyl-bis-carbamic acid dipentyl ester (including isomers),N,N′-hexanediyl-bis-carbamic acid dihexyl ester (including isomers),N,N′-hexanediyl-bis-carbamic acid dioctyl ester (including isomers),dimethyl-4,4′-methylene-dicyclohexyl carbamate,diethyl-4,4′-methylene-dicyclohexyl carbamate,dipropyl-4,4′-methylene-dicyclohexyl carbamate (including isomers),dibutyl-4,4′-methylene-dicyclohexyl carbamate (including isomers),dipentyl-4,4′-methylene-dicyclohexyl carbamate (including isomers),dihexyl-4,4′-methylene-dicyclohexyl carbamate (including isomers),diheptyl-4,4′-methylene-dicyclohexyl carbamate (including isomers),dioctyl-4,4′-methylene-dicyclohexyl carbamate (including isomers),3-(methoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamic acidmethyl ester, 3-(ethoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid ethyl ester,3-(propyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamicacid propyl ester (including isomers),3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamic acidbutyl ester (including isomers),3-(pentyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamicacid pentyl ester (including isomers),3-(hexyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamic acidhexyl ester (including isomers),3-(heptyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamicacid heptyl ester (including isomers),3-(octyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamic acidoctyl ester (including isomers), toluene-dicarbamic acid dimethyl ester(including isomers), toluene-dicarbamic acid diethyl ester (includingisomers), toluene-dicarbamic acid dipropyl ester (including isomers),toluene-dicarbamic acid dibutyl ester (including isomers),toluene-dicarbamic acid dipentyl ester (including isomers),toluene-dicarbamic acid dihexyl ester (including isomers),toluene-dicarbamic acid diheptyl ester (including isomers),toluene-dicarbamic acid dioctyl ester (including isomers),N,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid dimethyl ester,N,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid diethyl ester,N,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid dipropyl ester,N,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid dibutyl ester,N,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid dipentyl ester,N,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid dihexyl ester,N,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid diheptyl ester, orN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid dioctyl ester.

Among these, an alkyl carbamate in which R⁷ in formula (17) above is agroup selected from the group consisting of an alkyl group having 1 to20 carbon atoms and a cycloalkyl group having 5 to 20 carbon atoms isused preferably, while an alkyl carbamate represented by any of thefollowing formulas (18) to (20) is used particularly preferably:

(wherein R¹¹ has the same meaning as defined above).

Examples of alkyl polycarbamates represented by formula (18) may includeN,N′-hexanediyl-bis-carbamic acid dimethyl ester,N,N′-hexanediyl-bis-carbamic acid diethyl ester,N,N′-hexanediyl-bis-carbamic acid dibutyl ester (including isomers),N,N′-hexanediyl-bis-carbamic acid dipentyl ester (including isomers),N,N′-hexanediyl-bis-carbamic acid dihexyl ester (including isomers) andN,N′-hexanediyl-bis-carbamic acid dioctyl ester (including isomers). Inaddition, examples of alkyl polycarbamates represented by formula (19)may include dimethyl-4,4′-methylene-dicyclohexyl carbamate,diethyl-4,4′-methylene-dicyclohexyl carbamate,dipropyl-4,4′-methylene-dicyclohexyl carbamate (including isomers),dibutyl-4,4′-methylene-dicyclohexyl carbamate (including isomers),dipentyl-4,4′-methylene-dicyclohexyl carbamate (including isomers),dihexyl-4,4′-methylene-dicyclohexyl carbamate (including isomers),diheptyl-4,4′-methylene-dicyclohexyl carbamate (including isomers) anddioctyl-4,4′-methylene-dicyclohexyl carbamate (including isomers).Moreover, examples of alkyl polycarbamates represented by formula (20)may include alkyl polycarbamates such as3-(methoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamic acidmethyl ester, 3-(ethoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid ethyl ester,3-(propyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamicacid propyl ester (including isomers),3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamic acidbutyl ester (including isomers),3-(pentyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamicacid pentyl ester (including isomers),3-(hexyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamic acidhexyl ester (including isomers),3-(heptyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamicacid heptyl ester (including isomers) or3-(octyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamic acidoctyl ester (including isomers).

The known method can be used to produce the carbamic acid ester. Forexample, carbamic acid esters may be produced by reacting aminecompounds with carbon monoxide, oxygen and aliphatic alcohols oraromatic hydroxy compounds, reacting amine compounds with urea andaliphatic alcohols or aromatic hydroxy compounds, or reacting carbonicacid esters with amine compounds.

<Aromatic Hydroxy Compound>

There are no particular limitations on the aromatic hydroxy compound inthe present embodiment, it is preferably an aromatic hydroxy compound inwhich the normal boiling point of the aromatic hydroxy compound ishigher than the normal boiling point of a compound R¹¹OH having astructure in which a hydrogen atom has been added to R¹¹O (wherein Orepresents an oxygen atom) constituting an ester group of the carbamicacid ester represented by formula (17) above, more preferably anaromatic hydroxy compound in which the normal boiling point is 20° C. ormore higher than that of R¹¹OH, and even more preferably an aromatichydroxy compound in which the normal boiling point is 50° C. or morehigher than that of R¹¹OH. The term “normal boiling point” referredherein indicates the boiling point at one atmosphere.

In addition, the normal boiling point of the aromatic hydroxy compoundis preferably higher than the normal boiling point of a compoundR¹¹OCOOR¹¹ having a structure in which the group R¹¹O (wherein Orepresents an oxygen atom) constituting an ester group of a carbamicacid ester represented by formula (17) above is bonded through acarbonyl group, more preferably 10° C. or more higher than the normalboiling point of R¹¹OCOOR¹¹, and even more preferably 20° C. or morehigher than the normal boiling point of R¹¹OCOOR¹¹.

In this manner, although an aromatic hydroxy compound is preferably usedin which the normal boiling point thereof is higher than the normalboiling point of R¹¹OH or R¹¹OCOOR¹¹, this is for recovering a carbamicacid ester in the form of a composition with an aromatic hydroxycompound from a bottom of a distillation column during distillativeseparation with a distillation column of alcohol and/or carbonic acidester or urea in the presence of an aromatic hydroxy compound from amixture obtained in step (1) or step (2) above in a preferableproduction process of the composition of the present embodiment to bedescribed later.

In addition, the molecular weight of the aromatic hydroxy compound ispreferably within a range of from 120 to 370, and more preferably withina range of from 200 to 350, in consideration of the preferable normalboiling point range described above, and preventing an excessivedecrease in transfer efficiency due to an excessively low weightpercentage of carbamic acid ester in the composition of the presentembodiment.

Moreover, the aromatic hydroxy compound is preferably a compound havingone hydroxyl group directly bonded to an aromatic hydrocarbon ringconstituting the aromatic hydroxy compound. Although an aromatic hydroxycompound having two or more hydroxyl groups directly bonded to anaromatic hydrocarbon ring constituting the aromatic hydroxy compound canalso be used as the aromatic hydroxy compound constituting thecomposition of the present embodiment, since there are cases in whichthe viscosity of the composition may be high, this can lead to adecrease in efficiency during transfer.

Preferable examples of compounds used as such aromatic hydroxy compoundsmay include aromatic hydroxy compounds which are represented by thefollowing formula (21), and which have at least one substituent R¹:

(wherein ring A represents a single or multiple aromatic hydrocarbonring which have 6 to 20 carbon atoms, and which may have a substituent;

R¹ represents an aliphatic group having 1 to 20 carbon atoms, analiphatic alkoxy group having 1 to 20 carbon atoms, an aryl group having6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, anaralkyl group having 7 to 20 carbon atoms, or an aralkyloxy group having7 to 20 carbon atoms, the above groups containing an atom selected fromthe group consisting of carbon, oxygen and nitrogen atoms, and R¹ maybond with A to form a ring structure).

Examples of ring A in formula (21) above may include a benzene ring, anaphthalene ring, an anthracene ring, a phenanthrene ring, a naphthacenering, a chrysene ring, a pyrene ring, a triphenylene ring, a pentalenering, an azulene ring, a heptalene ring, an indacene ring, a biphenylenering, an acenaphthylene ring, an aceanthrylene ring and anacephenanthrylene ring. Preferable examples may include rings selectedfrom the group consisting of a benzene ring, a naphthalene ring and ananthracene ring. In addition, these rings may have a substituent otherthan the above-mentioned R¹, examples of which may include aliphaticalkyl groups in which the number of carbon atoms constituting the groupis a number selected from integers of 1 to 20, such as a methyl group,an ethyl group, a propyl group (including isomers), a butyl group(including isomers), a pentyl group (including isomers), a hexyl group(including isomers), a heptyl group (including isomers), an octyl group(including isomers), a nonyl group (including isomers), a decyl group(including isomers), a dodecyl group (including isomers) or an octadecylgroup (including isomers); aliphatic alkoxy groups in which the numberof carbon atoms constituting the group is a number selected fromintegers of 1 to 20, such as a methoxy group, an ethoxy group, a propoxygroup (including isomers), a butyloxy group (including isomers), apentyloxy group (including isomers), a hexyloxy group (includingisomers), a heptyloxy group (including isomers), an octyloxy group(including isomers), a nonyloxy group (including isomers), a decyloxygroup (including isomers), a dodecyloxy group (including isomers) or anoctadecyloxy group (including isomers); aryl groups in which the numberof carbon atoms constituting the group is 6 to 20, such as a phenylgroup, a methylphenyl group (including isomers), an ethylphenyl group(including isomers), a propylphenyl group (including isomers), abutylphenyl group (including isomers), a pentylphenyl group (includingisomers), a hexylphenyl group (including isomers), a heptylphenyl group(including isomers), an octylphenyl group (including isomers), anonylphenyl group (including isomers), a decylphenyl group (includingisomers), a biphenyl group (including isomers), a dimethylphenyl group(including isomers), a diethylphenyl group (including isomers), adipropylphenyl group (including isomers), a dibutylphenyl group(including isomers), a dipentylphenyl group (including isomers), adihexylphenyl group (including isomers), a diheptylphenyl group(including isomers), a terphenyl group (including isomers), atrimethylphenyl group (including isomers), a triethylphenyl group(including isomers), a tripropylphenyl group (including isomers) or atributylphenyl group (including isomers); aryloxy groups in which thenumber of carbon atoms constituting the group is 6 to 20, such as aphenoxy group, a methylphenoxy group (including isomers), anethylphenoxy group (including isomers), a propylphenoxy group (includingisomers), a butylphenoxy group (including isomers), a pentylphenoxygroup (including isomers), a hexylphenoxy group (including isomers), aheptylphenoxy group (including isomers), an octylphenoxy group(including isomers), a nonylphenoxy group (including isomers), adecylphenoxy group (including isomers), a phenylphenoxy group (includingisomers), a dimethylphenoxy group (including isomers), a diethylphenoxygroup (including isomers), a dipropylphenoxy group (including isomers),a dibutylphenoxy group (including isomers), a dipentylphenoxy group(including isomers), a dihexylphenoxy group (including isomers), adiheptylphenoxy group (including isomers), a diphenylphenoxy group(including isomers), a trimethylphenoxy group (including isomers), atriethylphenoxy group (including isomers), a tripropylphenoxy group(including isomers) or a tributylphenoxy group (including isomers);aralkyl groups in which the number of carbon atoms constituting thegroup is 7 to 20, such as a phenylmethyl group, a phenylethyl group(including isomers), a phenylpropyl group (including isomers), aphenylbutyl group (including isomers), a phenylpentyl group (includingisomers), a phenylhexyl group (including isomers), a phenylheptyl group(including isomers), a phenyloctyl group (including isomers) or aphenylnonyl group (including isomers); and aralkyloxy groups in whichthe number of carbon atoms constituting the group is 7 to 20, such as aphenylmethoxy group, a phenylethoxy group (including isomers), aphenylpropyloxy group (including isomers), a phenylbutyloxy group(including isomers), a phenylpentyloxy group (including isomers), aphenylhexyloxy group (including isomers), a phenylheptyloxy group(including isomers), a phenyloctyloxy group (including isomers) or aphenylnonyloxy group (including isomers). These groups are preferablygroups that do not contain atoms other than carbon, oxygen, nitrogen andhydrogen atoms.

Examples of R¹ in formula (21) above may include aliphatic alkyl groupsin which the number of carbon atoms constituting the group is a numberselected from integers of 1 to 20, such as a methyl group, an ethylgroup, a propyl group (including isomers), a butyl group (includingisomers), a pentyl group (including isomers), a hexyl group (includingisomers), a heptyl group (including isomers), an octyl group (includingisomers), a nonyl group (including isomers), a decyl group (includingisomers), a dodecyl group (including isomers) or an octadecyl group(including isomers); aliphatic alkoxy groups in which the number ofcarbon atoms constituting the group is a number selected from integersof 1 to 20, such as a methoxy group, an ethoxy group, a propoxy group(including isomers), a butyloxy group (including isomers), a pentyloxygroup (including isomers), a hexyloxy group (including isomers), aheptyloxy group (including isomers), an octyloxy group (includingisomers), a nonyloxy group (including isomers), a decyloxy group(including isomers), a dodecyloxy group (including isomers) or anoctadecyloxy group (including isomers); aryl groups in which the numberof carbon atoms constituting the group is 6 to 20, such as a phenylgroup, a methylphenyl group (including isomers), an ethylphenyl group(including isomers), a propylphenyl group (including isomers), abutylphenyl group (including isomers), a pentylphenyl group (includingisomers), a hexylphenyl group (including isomers), a heptylphenyl group(including isomers), an octylphenyl group (including isomers), anonylphenyl group (including isomers), a decylphenyl group (includingisomers), a biphenyl group (including isomers), a dimethylphenyl group(including isomers), a diethylphenyl group (including isomers), adipropylphenyl group (including isomers), a dibutylphenyl group(including isomers), a dipentylphenyl group (including isomers), adihexylphenyl group (including isomers), a diheptylphenyl group(including isomers), a terphenyl group (including isomers), atrimethylphenyl group (including isomers), a triethylphenyl group(including isomers), a tripropylphenyl group (including isomers) or atributylphenyl group (including isomers); aryloxy groups in which thenumber of carbon atoms constituting the group is 6 to 20, such as aphenoxy group, a methylphenoxy group (including isomers), anethylphenoxy group (including isomers), a propylphenoxy group (includingisomers), a butylphenoxy group (including isomers), a pentylphenoxygroup (including isomers), a hexylphenoxy group (including isomers), aheptylphenoxy group (including isomers), an octylphenoxy group(including isomers), a nonylphenoxy group (including isomers), adecylphenoxy group (including isomers), a phenylphenoxy group (includingisomers), a dimethylphenoxy group (including isomers), a diethylphenoxygroup (including isomers), a dipropylphenoxy group (including isomers),a dibutylphenoxy group (including isomers), a dipentylphenoxy group(including isomers), a dihexylphenoxy group (including isomers), adiheptylphenoxy group (including isomers), a diphenylphenoxy group(including isomers), a trimethylphenoxy group (including isomers), atriethylphenoxy group (including isomers), a tripropylphenoxy group(including isomers) or a tributylphenoxy group (including isomers);aralkyl groups in which the number of carbon atoms constituting thegroup is 7 to 20, such as a phenylmethyl group, a phenylethyl group(including isomers), a phenylpropyl group (including isomers), aphenylbutyl group (including isomers), a phenylpentyl group (includingisomers), a phenylhexyl group (including isomers), a phenylheptyl group(including isomers), a phenyloctyl group (including isomers) or aphenylnonyl group (including isomers); and aralkyloxy groups in whichthe number of carbon atoms constituting the group is 7 to 20, such as aphenylmethoxy group, a phenylethoxy group (including isomers), aphenylpropyloxy group (including isomers), a phenylbutyloxy group(including isomers), a phenylpentyloxy group (including isomers), aphenylhexyloxy group (including isomers), a phenylheptyloxy group(including isomers), a phenyloctyloxy group (including isomers) or aphenylnonyloxy group (including isomers). These groups are preferablygroups that do not contain atoms other than carbon, oxygen, nitrogen andhydrogen atoms.

Examples of such an aromatic hydroxy compound may include compoundsrepresented by the following formula (22):

(wherein each of R², R³, R⁴, R⁵ and R⁶ independently represents ahydrogen atom, or an aliphatic group having 1 to 20 carbon atoms, analiphatic alkoxy group having 1 to 20 carbon atoms, an aryl group having6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, anaralkyl group having 7 to 20 carbon atoms or an aralkyloxy group having7 to 20 carbon atoms, the above groups containing an atom selected fromthe group consisting of carbon, oxygen and nitrogen atoms, and at leastone of R², R³, R⁴, R⁵ and R⁶ does not represent a hydrogen atom).

Examples of R², R³, R⁴, R⁵ and R⁶ may include aliphatic alkyl groups inwhich the number of carbon atoms constituting the group is a numberselected from integers of 1 to 20, such as a methyl group, an ethylgroup, a propyl group (including isomers), a butyl group (includingisomers), a pentyl group (including isomers), a hexyl group (includingisomers), a heptyl group (including isomers), an octyl group (includingisomers), a nonyl group (including isomers), a decyl group (includingisomers), a dodecyl group (including isomers) or an octadecyl group(including isomers); aliphatic alkoxy groups in which the number ofcarbon atoms constituting the group is a number selected from integersof 1 to 20, such as a methoxy group, an ethoxy group, a propoxy group(including isomers), a butyloxy group (including isomers), a pentyloxygroup (including isomers), a hexyloxy group (including isomers), aheptyloxy group (including isomers), an octyloxy group (includingisomers), a nonyloxy group (including isomers), a decyloxy group(including isomers), a dodecyloxy group (including isomers) or anoctadecyloxy group (including isomers); aryl groups in which the numberof carbon atoms constituting the group is 6 to 20, such as a phenylgroup, a methylphenyl group (including isomers), an ethylphenyl group(including isomers), a propylphenyl group (including isomers), abutylphenyl group (including isomers), a pentylphenyl group (includingisomers), a hexylphenyl group (including isomers), a heptylphenyl group(including isomers), an octylphenyl group (including isomers), anonylphenyl group (including isomers), a decylphenyl group (includingisomers), a biphenyl group (including isomers), a dimethylphenyl group(including isomers), a diethylphenyl group (including isomers), adipropylphenyl group (including isomers), a dibutylphenyl group(including isomers), a dipentylphenyl group (including isomers), adihexylphenyl group (including isomers), a diheptylphenyl group(including isomers), a terphenyl group (including isomers), atrimethylphenyl group (including isomers), a triethylphenyl group(including isomers), a tripropylphenyl group (including isomers) or atributylphenyl group (including isomers); aryloxy groups in which thenumber of carbon atoms constituting the group is 6 to 20, such as aphenoxy group, a methylphenoxy group (including isomers), anethylphenoxy group (including isomers), a propylphenoxy group (includingisomers), a butylphenoxy group (including isomers), a pentylphenoxygroup (including isomers), a hexylphenoxy group (including isomers), aheptylphenoxy group (including isomers), an octylphenoxy group(including isomers), a nonylphenoxy group (including isomers), adecylphenoxy group (including isomers), a phenylphenoxy group (includingisomers), a dimethylphenoxy group (including isomers), a diethylphenoxygroup (including isomers), a dipropylphenoxy group (including isomers),a dibutylphenoxy group (including isomers), a dipentylphenoxy group(including isomers), a dihexylphenoxy group (including isomers), adiheptylphenoxy group (including isomers), a diphenylphenoxy group(including isomers), a trimethylphenoxy group (including isomers), atriethylphenoxy group (including isomers), a tripropylphenoxy group(including isomers) or a tributylphenoxy group (including isomers);aralkyl groups in which the number of carbon atoms constituting thegroup is 7 to 20, such as a phenylmethyl group, a phenylethyl group(including isomers), a phenylpropyl group (including isomers), aphenylbutyl group (including isomers), a phenylpentyl group (includingisomers), a phenylhexyl group (including isomers), a phenylheptyl group(including isomers), a phenyloctyl group (including isomers) or aphenylnonyl group (including isomers); and aralkyloxy groups in whichthe number of carbon atoms constituting the group is 7 to 20, such as aphenylmethoxy group, a phenylethoxy group (including isomers), aphenylpropyloxy group (including isomers), a phenylbutyloxy group(including isomers), a phenylpentyloxy group (including isomers), aphenylhexyloxy group (including isomers), a phenylheptyloxy group(including isomers), a phenyloctyloxy group (including isomers) or aphenylnonyloxy group (including isomers).

Examples of aromatic hydroxy compounds may include mono-substitutedphenols such as ethylphenol (including isomers), propylphenol (includingisomers), butylphenol (including isomers), pentylphenol (includingisomers), hexylphenol (including isomers), heptylphenol (includingisomers), octylphenol (including isomers), nonylphenol (includingisomers), decylphenol (including isomers), dodecylphenol (includingisomers), phenylphenol (including isomers), phenoxyphenol (includingisomers) or cumylphenol (including isomers); di-substituted phenols suchas dimethylphenol (including isomers), diethylphenol (includingisomers), dipropylphenol (including isomers), dibutylphenol (includingisomers), dipentylphenol (including isomers), dihexylphenol (includingisomers), diheptylphenol (including isomers), dioctylphenol (includingisomers), dinonylphenol (including isomers), didecylphenol (includingisomers), didodecylphenol (including isomers), diphenylphenol (includingisomers), diphenoxyphenol (including isomers), dicumylphenol (includingisomers), methylethylphenol (including isomers), methylpropylphenol(including isomers), methylbutylphenol (including isomers),methylpentylphenol (including isomers), methylhexylphenol (includingisomers), methylheptylphenol (including isomers), methyloctylphenol(including isomers), methylnonylphenol (including isomers),methyldecylphenol (including isomers), methyldodecylphenol (includingisomers), methylphenylphenol (including isomers), methylphenoxyphenol(including isomers), methylcumylphenol (including isomers),ethylpropylphenol (including isomers), ethylbutylphenol (includingisomers), ethylpentylphenol (including isomers), ethylhexylphenol(including isomers), ethylheptylphenol (including isomers),ethyloctylphenol (including isomers), ethylnonylphenol (includingisomers), ethyldecylphenol (including isomers), ethyldodecylphenol(including isomers), ethylphenylphenol (including isomers),ethylphenoxyphenol (including isomers), ethylcumylphenol (includingisomers), propylbutylphenol (including isomers), propylpentylphenol(including isomers), propylhexylphenol (including isomers),propylheptylphenol (including isomers), propyloctylphenol (includingisomers), propylnonylphenol (including isomers), propyldecylphenol(including isomers), propyldodecylphenol (including isomers),propylphenylphenol (including isomers), propylphenoxyphenol (includingisomers), propylcumylphenol (including isomers), butylpentylphenol(including isomers), butylhexylphenol (including isomers),butylheptylphenol (including isomers), butyloctylphenol (includingisomers), butylnonylphenol (including isomers), butyldecylphenol(including isomers), butyldodecylphenol (including isomers),butylphenylphenol (including isomers), butylphenoxyphenol (includingisomers), butylcumylphenol (including isomers), pentylhexylphenol(including isomers), pentylheptylphenol (including isomers),pentyloctylphenol (including isomers), pentylnonylphenol (includingisomers), pentyldecylphenol (including isomers), pentyldodecylphenol(including isomers), pentylphenylphenol (including isomers),pentylphenoxyphenol (including isomers), pentylcumylphenol (includingisomers), hexylheptylphenol (including isomers), hexyloctylphenol(including isomers), hexylnonylphenol (including isomers),hexyldecylphenol (including isomers), hexyldodecylphenol (includingisomers), hexylphenylphenol (including isomers), hexylphenoxyphenol(including isomers), hexylcumylphenol (including isomers),heptyloctylphenol (including isomers), heptylnonylphenol (includingisomers), heptyldecylphenol (including isomers), heptyldodecylphenol(including isomers), heptylphenylphenol (including isomers),heptylphenoxyphenol (including isomers), heptylcumylphenol (includingisomers), octylnonylphenol (including isomers), octyldecylphenol(including isomers), octyldodecylphenol (including isomers),octylphenylphenol (including isomers), octylphenoxyphenol (includingisomers), octylcumylphenol (including isomers), nonyldecylphenol(including isomers), nonyldodecylphenol (including isomers),nonylphenylphenol (including isomers), nonylphenoxyphenol (includingisomers), nonylcumylphenol (including isomers), dodecylphenylphenol(including isomers), dodecylphenoxyphenol (including isomers) ordodecylcumylphenol (including isomers); and, tri-substituted phenolssuch as trimethylphenol (including isomers), triethylphenol (includingisomers), tripropylphenol (including isomers), tributylphenol (includingisomers), tripentylphenol (including isomers), trihexylphenol (includingisomers), triheptylphenol (including isomers), trioctylphenol (includingisomers), trinonylphenol (including isomers), tridecylphenol (includingisomers), tridodecylphenol (including isomers), triphenylphenol(including isomers), triphenoxyphenol (including isomers),tricumylphenol (including isomers), dimethylethylphenol (includingisomers), dimethylpropylphenol (including isomers), dimethylbutylphenol(including isomers), dimethylpentylphenol (including isomers),dimethylhexylphenol (including isomers), dimethylheptylphenol (includingisomers), dimethyloctylphenol (including isomers), dimethylnonylphenol(including isomers), dimethyldecylphenol (including isomers),dimethyldodecylphenol (including isomers), dimethylphenylphenol(including isomers), dimethylphenoxyphenol (including isomers),dimethylcumylphenol (including isomers), diethylmethylphenol (includingisomers), diethylpropylphenol (including isomers), diethylbutylphenol(including isomers), diethylpentylphenol (including isomers),diethylhexylphenol (including isomers), diethylheptylphenol (includingisomers), diethyloctylphenol (including isomers), diethylnonylphenol(including isomers), diethyldecylphenol (including isomers),diethyldodecylphenol (including isomers), diethylphenylphenol (includingisomers), diethylphenoxyphenol (including isomers), diethylcumylphenol(including isomers), dipropylmethylphenol (including isomers),dipropylethylphenol (including isomers), dipropylbutylphenol (includingisomers), dipropylpentylphenol (including isomers), dipropylhexylphenol(including isomers), dipropylheptylphenol (including isomers),dipropyloctylphenol (including isomers), dipropylnonylphenol (includingisomers), dipropyldecylphenol (including isomers), dipropyldodecylphenol(including isomers), dipropylphenylphenol (including isomers),dipropylphenoxyphenol (including isomers), dipropylcumylphenol(including isomers), dibutylmethylphenol (including isomers),dibutylethylphenol (including isomers), dibutylpropylphenol (includingisomers), dibutylpentylphenol (including isomers), dibutylhexylphenol(including isomers), dibutylheptylphenol (including isomers),dibutylocylphenol (including isomers), dibutylnonylphenol (includingisomers), dibutyldecylphenol (including isomers), dibutyldodecylphenol(including isomers), dibutylphenylphenol (including isomers),dibutylphenoxyphenol (including isomers), dibutylcumylphenol (includingisomers), dipentylmethylphenol (including isomers), dipentylethylphenol(including isomers), dipentylpropylphenol (including isomers),dipentylbutylphenol (including isomers), dipentylhexylphenol (includingisomers), dipentylheptylphenol (including isomers), dipentyloctylphenol(including isomers), dipentylnonylphenol (including isomers),dipentyldecylphenol (including isomers), dipentyldodecylphenol(including isomers), dipentylphenylphenol (including isomers),dipentylphenoxyphenol (including isomers), dipentylcumylphenol(including isomers), dihexylmethylphenol (including isomers),dihexylethylphenol (including isomers), dihexylpropylphenol (includingisomers), dihexylbutylphenol (including isomers), dihexylpentylphenol(including isomers), dihexylheptylphenol (including isomers),dihexyloctylphenol (including isomers), dihexylnonylphenol (includingisomers), dihexyldecylphenol (including isomers), dihexyldodecylphenol(including isomers), dihexylphenylphenol (including isomers),dihexylphenoxyphenol (including isomers), dihexylcumylphenol (includingisomers), diheptylmethylphenol (including isomers), diheptylethylphenol(including isomers), diheptylpropylphenol (including isomers),diheptylbutylphenol (including isomers), diheptylpentylphenol (includingisomers), diheptylhexylphenol (including isomers), diheptyloctylphenol(including isomers), diheptylnonylphenol (including isomers),diheptyldecylphenol (including isomers), diheptyldodecylphenol(including isomers), diheptylphenylphenol (including isomers),diheptylphenoxyphenol (including isomers), diheptylcumylphenol(including isomers), dioctylmethylphenol (including isomers),dioctylethylphenol (including isomers), dioctylpropylphenol (includingisomers), dioctylbutylphenol (including isomers), dioctylpentylphenol(including isomers), dioctylhexylphenol (including isomers),dioctylheptylphenol (including isomers), dioctylnonylphenol (includingisomers), dioctyldecylphenol (including isomers), dioctyldodecylphenol(including isomers), dioctylphenylphenol (including isomers),dioctylphenoxyphenol (including isomers), dioctylcumylphenol (includingisomers), dinonylmethylphenol (including isomers), dinonylethylphenol(including isomers), dinonylpropylphenol (including isomers),dinonylbutylphenol (including isomers), dinonylpentylphenol (includingisomers), dinonylhexylphenol (including isomers), dinonylheptylphenol(including isomers), dinonyloctylphenol (including isomers),dinonyldecylphenol (including isomers), dinonyldodecylphenol (includingisomers), dinonylphenylphenol (including isomers), dinonylphenoxyphenol(including isomers), dinonylcumylphenol (including isomers),didecylmethylphenol (including isomers), didecylethylphenol (includingisomers), didecylpropylphenol (including isomers), didecylbutylphenol(including isomers), didecylpentylphenol (including isomers),didecylhexylphenol (including isomers), didecylheptylphenol (includingisomers), didecyloctylphenol (including isomers), didecylnonylphenol(including isomers), didecyldodecylphenol (including isomers),didecylphenylphenol (including isomers), didecylphenoxyphenol (includingisomers), didecylcumylphenol (including isomers), didodecylmethylphenol(including isomers), didodecylethylphenol (including isomers),didodecylpropylphenol (including isomers), didodecylbutylphenol(including isomers), didodecylpentylphenol (including isomers),didodecylhexylphenol (including isomers), didodecylheptylphenol(including isomers), didodecyloctylphenol (including isomers),didodecylnonylphenol (including isomers), didodecyldecylphenol(including isomers), didodecyldodecylphenol (including isomers),didodecylphenylphenol (including isomers), didodecylphenoxyphenol(including isomers), didodecylcumylphenol (including isomers),diphenylmethylphenol (including isomers), diphenylethylphenol (includingisomers), diphenylpropylphenol (including isomers), diphenylbutylphenol(including isomers), diphenylpentylphenol (including isomers),diphenylhexylphenol (including isomers), diphenylheptylphenol (includingisomers), diphenyloctylphenol (including isomers), diphenylnonylphenol(including isomers), diphenyldecylphenol (including isomers),diphenyldodecylphenol (including isomers), diphenylphenoxyphenol(including isomers), diphenylcumylphenol (including isomers),diphenoxymethylphenol (including isomers), diphenoxyethylphenol(including isomers), diphenoxypropylphenol (including isomers),diphenoxybutylphenol (including isomers), diphenoxypentylphenol(including isomers), diphenoxyhexylphenol (including isomers),diphenoxyheptylphenol (including isomers), diphenoxyoctylphenol(including isomers), diphenoxynonylphenol (including isomers),diphenoxydecylphenol (including isomers), diphenoxydodecylphenol(including isomers), diphenoxyphenylphenol (including isomers),diphenoxycumylphenol (including isomers), dicumylmethylphenol (includingisomers), dicumylethylphenol (including isomers), dicumylpropylphenol(including isomers), dicumylbutylphenol (including isomers),dicumylpentylphenol (including isomers), dicumylhexylphenol (includingisomers), dicumylheptylphenol (including isomers), dicumyloctylphenol(including isomers), dicumylnonylphenol (including isomers),dicumyldecylphenol (including isomers), dicumyldodecylphenol (includingisomers), dicumylphenylphenol (including isomers), dicumylphenoxyphenol(including isomers), methylethylpropylphenol (including isomers),methylethylbutylphenol (including isomers), methylethylpentylphenol(including isomers), methylethylhexylphenol (including isomers),methylethylheptylphenol (including isomers), methylethyloctylphenol(including isomers), methylethylnonylphenol (including isomers),methylethyldecylphenol (including isomers), methylethyldodecylphenol(including isomers), methylethylphenylphenol (including isomers),methylethylphenoxyphenol (including isomers), methylethylcumylphenol(including isomers), methylpropylbutylphenol (including isomers),methylpropylpentylphenol (including isomers), methylpropylhexylphenol(including isomers), methylpropylheptylphenol (including isomers),methylpropyloctylphenol (including isomers), methylpropylnonylphenol(including isomers), methylpropyldecylphenol (including isomers),methylpropyldodecylphenol (including isomers), methylpropylphenylphenol(including isomers), methylpropylphenoxyphenol (including isomers),methylpropylcumylphenol (including isomers), methylbutylpentylphenol(including isomers), methylbutylhexylphenol (including isomers),methylbutylheptylphenol (including isomers), methylbutyloctylphenol(including isomers), methylbutylnonylphenol (including isomers),methylbutyldecylphenol (including isomers), methylbutyldodecylphenol(including isomers), methylbutylphenylphenol (including isomers),methylbutylphenoxyphenol (including isomers), methylbutylcumylphenol(including isomers), methylpentylhexylphenol, methylpentylheptylphenol(including isomers), methylpentyloctylphenol (including isomers),methylpentylnonylphenol (including isomers), methylpentyldecylphenol(including isomers), methylpentyldodecylphenol (including isomers),methylpentylphenylphenol (including isomers), methylpentylphenoxyphenol(including isomers), methylpentylcumylphenol (including isomers),methylhexylheptylphenol (including isomers), methylhexyloctylphenol(including isomers), methylhexylnonylphenol (including isomers),methylhexyldecylphenol (including isomers), methylhexyldodecylphenol(including isomers), methylhexylphenylphenol (including isomers),methylhexylphenoxyphenol (including isomers), methylhexylcumylphenol(including isomers), ethylpropylbutylphenol (including isomers),ethylpropylpentylphenol (including isomers), ethylpropylhexylphenol(including isomers), ethylpropylheptylphenol (including isomers),ethylpropyloctyl phenol (including isomers), ethylpropylnonylphenol(including isomers), ethylpropyldecylphenol (including isomers),ethylpropyldodecylphenol (including isomers), ethylpropylphenylphenol(including isomers), ethylpropylphenoxyphenol (including isomers),ethylpropylcumylphenol (including isomers), ethylbutylphenol (includingisomers), ethylbutylpentylphenol (including isomers),ethylbutylhexylphenol (including isomers), ethylbutylheptylphenol(including isomers), ethylbutyloctylphenol (including isomers),ethylbutylnonylphenol (including isomers), ethylbutyldecylphenol(including isomers), ethylbutyldodecylphenol (including isomers),ethylbutylphenylphenol (including isomers), ethylbutylphenoxyphenol(including isomers), ethylbutylcumylphenol (including isomers),ethylpentylhexylphenol (including isomers), ethylpentylheptylphenol(including isomers), ethylpentyloctylphenol (including isomers),ethylpentylnonylphenol (including isomers), ethylpentyldecylphenol(including isomers), ethylpentyldodecylphenol (including isomers),ethylpentylphenylphenol (including isomers), ethylpentylphenoxyphenol(including isomers), ethylpentylcumylphenol (including isomers),ethylhexylheptylphenol (including isomers), ethylhexyloctylphenol(including isomers), ethylhexylnonylphenol (including isomers),ethylhexyldecylphenol (including isomers), ethylhexyldodecylphenol(including isomers), ethylhexylphenylphenol (including isomers),ethylhexylphenoxyphenol (including isomers), ethylhexylcumylphenol(including isomers), ethylheptyloctylphenol (including isomers),ethylheptylnonylphenol (including isomers), ethylheptyldecylphenol(including isomers), ethylheptyldodecylphenol (including isomers),ethylheptylphenylphenol (including isomers), ethylheptylphenoxyphenol(including isomers), ethylheptylcumylphenol (including isomers),ethyloctylphenol (including isomers), ethyloctylnonylphenol (includingisomers), ethylocyldecylphenol (including isomers),ethyloctyldodecylphenol (including isomers), ethyloctylphenylphenol(including isomers), ethyloctylphenoxyphenol (including isomers),ethyloctylcumylphenol (including isomers), ethylnonyldecylphenol(including isomers), ethylnonyldodecylphenol (including isomers),ethylnonylphenylphenol (including isomers), ethylnonylphenoxyphenol(including isomers), ethylnonylcumylphenol (including isomers),ethyldecyldodecylphenol (including isomers), ethyldecylphenylphenol(including isomers), ethyldecylphenoxyphenol (including isomers),ethyldecylcumylphenol (including isomers), ethyldodecylphenylphenol(including isomers), ethyldodecylphenoxyphenol (including isomers),ethyldodecylcumylphenol (including isomers), ethylphenylphenoxyphenol(including isomers), ethylphenylcumylphenol (including isomers),propylbutylphenol (including isomers), propylbutylpentylphenol(including isomers), propylbutylhexylphenol (including isomers),propylbutylheptylphenol (including isomers), propylbutyloctylphenol(including isomers), propylbutylnonylphenol (including isomers),propylbutyldecylphenol (including isomers), propylbutyldodecylphenol(including isomers), propylbutylphenylphenol (including isomers),propylbutylphenoxyphenol (including isomers), propylbutylcumylphenol(including isomers), propylpentylphenol (including isomers),propylpentylhexylphenol (including isomers), propylpentylheptylphenol(including isomers), propylpentyloctylphenol (including isomers),propylpentylnonylphenol (including isomers), propylpentyldecylphenol(including isomers), propylpentyldodecylphenol (including isomers),propylpentylphenylphenol (including isomers), propylpentylphenoxyphenol(including isomers), propylpentylcumylphenol (including isomers),propylhexylphenol (including isomers), propylhexylheptylphenol(including isomers), propylhexyloctylphenol (including isomers),propylhexylnonylphenol (including isomers), propylhexyldecylphenol(including isomers), propylhexyldodecylphenol (including isomers),propylhexylphenylphenol (including isomers), propylhexylphenoxyphenol(including isomers), propylhexylcumylphenol (including isomers),propylheptyloctylphenol (including isomers), propylheptylnonylphenol(including isomers), propylheptyldecylphenol (including isomers),propylheptyldodecylphenol (including isomers), propylheptylphenylphenol(including isomers), propylheptylphenoxyphenol (including isomers),propylheptylcumylphenol (including isomers), propyloctylnonylphenol(including isomers), propyloctyldecylphenol (including isomers),propyloctyldodecylphenol (including isomers), propyloctylphenylphenol(including isomers), propyloctylphenoxyphenol (including isomers),propyloctylcumylphenol (including isomers), propylnonyldecylphenol(including isomers), propylnonyldodecylphenol (including isomers),propylnonylphenylphenol (including isomers), propylnonylphenoxyphenol(including isomers), propylnonylcumylphenol (including isomers),propyldecyldodecylphenol (including isomers), propyldecylphenylphenol(including isomers), propyldecylphenoxyphenol (including isomers),propyldecylcumylphenol (including isomers), propyldodecylphenylphenol(including isomers), propyldodecylphenoxyphenol (including isomers),propyldodecylcumylphenol (including isomers), methylphenol (includingisomers), ethylphenol (including isomers), propylphenol (includingisomers), butylphenol (including isomers), pentylphenol (includingisomers), hexylphenol (including isomers), heptylphenol (includingisomers), octylphenol (including isomers), nonylphenol (includingisomers), decylphenol (including isomers), dodecylphenol (includingisomers), phenylphenol (including isomers), phenoxyphenol (includingisomers), cumylphenol (including isomers), propylphenylphenoxyphenol(including isomers), propylphenylcumylphenol (including isomers),propylphenoxycumylphenol (including isomers), propylbutylpentylphenol(including isomers), propylbutylhexylphenol (including isomers),propylbutylheptylphenol (including isomers), propylbutyloctylphenol(including isomers), propylbutylnonylphenol (including isomers),propylbutyldecylphenol (including isomers), propylbutyldodecylphenol(including isomers), propylbutylphenylphenol (including isomers),propylbutylphenoxyphenol (including isomers), propylbutylcumylphenol(including isomers), propylpentylphenol (including isomers),propylpentylhexylphenol (including isomers), propylpentylheptylphenol(including isomers), propylpentyloctylphenol (including isomers),propylpentylnonylphenol (including isomers), propylpentyldecylphenol(including isomers), propylpentyldodecylphenol (including isomers),propylpentylphenylphenol (including isomers), propylpentylphenoxyphenol(including isomers), propylpentylcumylphenol (including isomers),propylhexylheptylphenol (including isomers), propylhexyloctylphenol(including isomers), propylhexylnonylphenol (including isomers),propylhexyldecylphenol (including isomers), propylhexyldodecylphenol(including isomers), propylhexylphenylphenol (including isomers),propylhexylphenoxyphenol (including isomers), propylhexylcumylphenol(including isomers), propylheptyloctylphenol (including isomers),propylheptylnonylphenol (including isomers), propylheptyldecylphenol(including isomers), propylheptyldodecylphenol (including isomers),propylheptylphenylphenol (including isomers), propylheptylphenoxyphenol(including isomers), propylheptylcumylphenol (including isomers),propyloctylnonylphenol (including isomers), propyloctyldecylphenol(including isomers), propyloctyldodecylphenol (including isomers),propyloctylphenylphenol (including isomers), propyloctylphenoxyphenol(including isomers), propyloctylcumylphenol (including isomers),propylnonyldecylphenol (including isomers), propylnonyldodecylphenol(including isomers), propylnonylphenylphenol (including isomers),propylnonylphenoxyphenol (including isomers), propylnonylcumylphenol(including isomers), propyldecyldodecylphenol (including isomers),propyldecylphenylphenol (including isomers), propyldecylphenoxyphenol(including isomers), propyldecylcumylphenol (including isomers),propyldodecylphenylphenol (including isomers),propyldodecylphenoxyphenol (including isomers), cumylphenol (includingisomers), propylphenylphenoxyphenol (including isomers),propylphenylcumylphenol (including isomers), butylpentylhexylphenol(including isomers), butylpentylheptylphenol (including isomers),butylpentyloctylphenol (including isomers), butylpentylnonylphenol(including isomers), butylpentyldecylphenol (including isomers),butylpentyldodecylphenol (including isomers), butylpentylphenylphenol(including isomers), butylpentylphenoxyphenol (including isomers),butylpentylcumylphenol (including isomers), butylhexylheptylphenol(including isomers), butylhexyloctylphenol (including isomers),butylhexylnonylphenol (including isomers), butylhexyldecylphenol(including isomers), butylhexyldodecylphenol (including isomers),butylhexylphenylphenol (including isomers), butylhexylphenoxyphenol(including isomers), butylhexylcumylphenol (including isomers),butylheptyloctylphenol (including isomers), butylheptylnonylphenol(including isomers), butylheptyldecylphenol (including isomers),butylheptyldodecylphenol (including isomers), butylheptylphenylphenol(including isomers), butylheptylphenoxyphenol (including isomers),butylheptylcumylphenol (including isomers), butyloctylnonylphenol(including isomers), butyloctyldecylphenol (including isomers),butyloctyldodecylphenol (including isomers), butyloctylphenylphenol(including isomers), butyloctylphenoxyphenol (including isomers),butyloctylcumylphenol (including isomers), butylnonyldecylphenol(including isomers), butylnonyldodecylphenol (including isomers),butylnonylphenylphenol (including isomers), butylnonylphenoxyphenol(including isomers), butylnonylcumylphenol (including isomers),butyldecyldodecylphenol (including isomers), butyldecylphenylphenol(including isomers), butyldecylphenoxyphenol (including isomers),butyldecylcumylphenol (including isomers), butyldodecylphenol (includingisomers), butyldodecylphenylphenol (including isomers),butyldodecylphenoxyphenol (including isomers), butyldodecylcumylphenol(including isomers), butylphenylphenol (including isomers),butylphenylphenoxyphenol (including isomers), butylphenylcumylphenol(including isomers), pentylhexylheptylphenol (including isomers),pentylhexyloctylphenol (including isomers), pentylhexylnonylphenol(including isomers), pentylhexyldecylphenol (including isomers),pentylhexyldodecylphenol (including isomers), pentylhexylphenylphenol(including isomers), pentylhexylphenoxyphenol (including isomers),pentylhexylcumylphenol (including isomers), pentylhetpyloctylphenol(including isomers), pentylheptylnonylphenol (including isomers),pentylheptyldecylphenol (including isomers), pentylheptyldodecylphenol(including isomers), pentylheptylphenylphenol (including isomers),pentylheptylphenoxyphenol (including isomers), pentylheptylcumylphenol(including isomers), pentyloctylnonylphenol (including isomers),pentyloctyldecylphenol (including isomers), pentyloctyldodecylphenol(including isomers), pentyloctylphenylphenol (including isomers),pentyloctylphenoxyphenol (including isomers), pentyloctylcumylphenol(including isomers), pentylnonyldecylphenol (including isomers),pentylnonyldodecylphenol (including isomers), pentylnonylphenylphenol(including isomers), pentylnonylphenoxyphenol (including isomers),pentylnonylcumylphenol (including isomers), pentyldecyldodecylphenol(including isomers), pentyldecylphenylphenol (including isomers),pentyldecylphenoxyphenol (including isomers), pentyldecylcumylphenol(including isomers), pentyldodecylphenylphenol (including isomers),pentyldodecylphenoxyphenol (including isomers), pentyldodecylcumylphenol(including isomers), pentylphenylphenoxyphenol (including isomers),pentylphenylcumylphenol (including isomers), hexylheptyloctylphenol(including isomers), hexylheptylnonylphenol (including isomers),hexylheptyldecylphenol (including isomers), hexylheptyldodecylphenol(including isomers), hexylheptylphenylphenol (including isomers),hexylheptylphenoxyphenol (including isomers), hexylheptylcumylphenol(including isomers), hexyloctylnonylphenol (including isomers),hexyloctyldecylphenol (including isomers), hexyloctyldodecylphenol(including isomers), hexyloctylphenylphenol (including isomers),hexyloctylphenoxyphenol (including isomers), hexyloctylcumylphenol(including isomers), hexylnonyldecylphenol (including isomers),hexylnonyldodecylphenol (including isomers), hexylnonylphenylphenol(including isomers), hexylnonylphenoxyphenol (including isomers),hexyldecyldodecylphenol (including isomers), hexyldecylphenylphenol(including isomers), hexyldecylphenoxyphenol (including isomers),hexyldecylcumylphenol (including isomers), hexyldodecylphenylphenol(including isomers), hexyldodecylphenoxyphenol (including isomers),hexyldodecylcumylphenol (including isomers), hexylphenylphenoxyphenol(including isomers), hexylphenylcumylphenol (including isomers),heptyloctylnonylphenol (including isomers), heptyloctyldecylphenol(including isomers), heptyloctyldodecylphenol (including isomers),heptyloctylphenylphenol (including isomers), heptyloctylphenoxyphenol(including isomers), heptyloctylcumylphenol (including isomers),heptylnonyldecylphenol (including isomers), heptylnonyldodecylphenol(including isomers), heptylnonylphenylphenol (including isomers),heptylnonylphenoxyphenol (including isomers), heptylnonylcumylphenol(including isomers), heptyldecyldodecylphenol (including isomers),heptyldecylphenylphenol (including isomers), heptyldecylphenoxyphenol(including isomers), heptyldecylcumylphenol (including isomers),heptyldodecylphenylphenol (including isomers),heptyldodecylphenoxyphenol (including isomers), heptyldodecylcumylphenol(including isomers), heptylphenylphenoxyphenol (including isomers),heptylphenylcumylphenol (including isomers), octylnonyldecylphenol(including isomers), octylnonyldodecylphenol (including isomers),octylnonylphenylphenol (including isomers), octylnonylphenoxyphenol(including isomers), octylnonylcumylphenol (including isomers),octyldecyldodecylphenol (including isomers), octyldecylphenylphenol(including isomers), octyldecylphenoxyphenol (including isomers),octyldecylcumylphenol (including isomers), octyldodecylphenylphenol(including isomers), octyldodecylphenoxyphenol (including isomers),octyldodecylcumylphenol (including isomers), octylphenylphenoxyphenol(including isomers), octylphenylcumylphenol (including isomers),nonyldecyldodecylphenol (including isomers), nonyldecylphenylphenol(including isomers), nonyldecylphenoxyphenol (including isomers),nonyldecylcumylphenol (including isomers), nonyldodecylphenylphenol(including isomers), nonyldodecylphenoxyphenol (including isomers),nonyldodecylcumylphenol (including isomers), nonylphenylphenoxyphenol(including isomers), nonylphenylcumylphenol (including isomers),decyldodecylphenylphenol (including isomers), decyldodecylphenoxyphenol(including isomers), decyldodecylcumylphenol (including isomers),decylphenylphenoxyphenol (including isomers), decylphenylcumylphenol(including isomers), dodecylphenylphenoxyphenol (including isomers),dodecylphenylcumylphenol (including isomers) or phenylphenoxycumylphenol(including isomers). One type of these aromatic hydroxy compounds may beused or a plurality of types may be used in combination.

The inventors of the present invention surprisingly found that thecarbamic acid ester does not undergo the thermal denaturation reactionas described above and is stable in the presence of the aromatic hydroxycompound. Although the mechanism by which denaturation of carbamic acidester is inhibited is not clear, the inventors of the present inventionpresumed that, for example, ester groups of the carbamic acid ester andthe aromatic hydroxy compound form hydrogen bonds, and correspondingester groups are inhibited from approaching each other by the hydrogenbonds, thereby inhibiting a decarboxylation reaction by correspondingester groups of the carbamic acid ester as shown in formula (2) above.In addition, even more unexpectedly, the temperature at which thecomposition of the present embodiment, comprising the carbamic acidester and the aromatic hydroxy compound, is a liquid is lower than themelting point of the carbamic acid ester as well as the melting point ofthe aromatic hydroxy compound, and since the composition can be held ata comparatively low temperature during transfer or storage in liquidform, the effect is also demonstrated by which the thermal denaturationreaction of the carbamic acid ester as described above is inhibited.

Among these aromatic hydroxy compounds, aromatic hydroxy compoundsrepresented by formula (22) above in which R⁴ is a group other than ahydrogen atom are used preferably, while aromatic hydroxy compoundsrepresented by formula (22) above in which the total number of carbonatoms constituting R² and R⁶ is 2 to 20 are even more preferable. Thereare no particular limitations on the combination of R⁴ and R⁸ providedthe total number of carbon atoms constituting R² and R⁶ is 2 to 20.

Even more preferably, each of R² and R⁴ in formula (22) aboveindependently represents a group represented by the following formula(23), and aromatic hydroxy compounds in which R³, R⁵ and R⁶ are hydrogenatoms, or aromatic hydroxy compounds in which R² in formula (22) aboveis a linear or branched alkyl group having 1 to 8 carbon atoms, and eachof R⁴ and R⁶ independently represents a hydrogen atom or a linear orbranched alkyl group having 1 to 8 carbon atoms, is used preferably:

(wherein X represents a single branched structure selected fromstructures represented by the following formulas (24) and (25));

(wherein R¹² represents a linear or branched alkyl group having 1 to 3carbon atoms).

Examples of such aromatic hydroxy compounds may include 2-ethylphenol,2-propylphenol (including isomers), 2-butylphenol (including isomers),2-pentylphenol (including isomers), 2-hexylphenol (including isomers),2-heptylphenol (including isomers), 2,6-dimethylphenol,2,4-diethylphenol, 2,6-diethylphenol, 2,4-dipropylphenol (includingisomers), 2,6-dipropylphenol (including isomers), 2,4-dibutylphenol(including isomers), 2,4-dipentylphenol (including isomers),2,4-dihexylphenol (including isomers), 2,4-diheptylphenol (includingisomers), 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol (includingisomers), 2-methyl-6-butylphenol (including isomers),2-methyl-6-pentylphenol (including isomers), 2-ethyl-6-propylphenol(including isomers), 2-ethyl-6-butylphenol (including isomers),2-ethyl-6-pentylphenol (including isomers), 2-propyl-6-butylphenol(including isomers), 2-ethyl-4-methylphenol (including isomers),2-ethyl-4-propylphenol (including isomers), 2-ethyl-4-butylphenol(including isomers), 2-ethyl-4-pentylphenol (including isomers),2-ethyl-4-hexylphenol (including isomers), 2-ethyl-4-heptylphenol(including isomers), 2-ethyl-4-octylphenol (including isomers),2-ethyl-4-phenylphenol (including isomers), 2-ethyl-4-cumylphenol(including isomers), 2-propyl-4-methylphenol (including isomers),2-propyl-4-ethylphenol (including isomers), 2-propyl-4-butylphenol(including isomers), 2-propyl-4-pentylphenol (including isomers),2-propyl-4-hexylphenol (including isomers), 2-propyl-4-hetpylphenol(including isomers), 2-propyl-4-octylphenol (including isomers),2-propyl-4-phenylphenol (including isomers), 2-propyl-4-cumylphenol(including isomers), 2-butyl-4-methylphenol (including isomers),2-butyl-4-ethylphenol (including isomers), 2-butyl-4-propylphenol(including isomers), 2-butyl-4-pentylphenol (including isomers),2-butyl-4-hexylphenol (including isomers), 2-butyl-4-heptylphenol(including isomers), 2-butyl-4-octylphenol (including isomers),2-butyl-4-phenylphenol (including isomers), 2-butyl-4-cumylphenol(including isomers), 2-pentyl-4-methylphenol (including isomers),2-pentyl-4-ethylphenol (including isomers), 2-pentyl-4-propylphenol(including isomers), 2-pentyl-4-butylphenol (including isomers),2-pentyl-4-hexylphenol (including isomers), 2-pentyl-4-heptylphenol(including isomers), 2-pentyl-4-octylphenol (including isomers),2-pentyl-4-phenylphenol (including isomers), 2-pentyl-4-cumylphenol(including isomers), 2-hexyl-4-methylphenol (including isomers),2-hexyl-4-ethylphenol (including isomers), 2-hexyl-4-propylphenol(including isomers), 2-hexyl-4-butylphenol (including isomers),2-hexyl-4-pentylphenol (including isomers), 2-hexyl-4-heptylphenol(including isomers), 2-hexyl-4-octylphenol (including isomers),2-hexyl-4-phenylphenol (including isomers), 2-hexyl-4-cumylphenol(including isomers), 2-heptyl-4-methylphenol (including isomers),2-heptyl-4-ethylphenol (including isomers), 2-heptyl-4-propylphenol(including isomers), 2-heptyl-4-butylphenol (including isomers),2-heptyl-4-pentylphenol (including isomers), 2-heptyl-4-hexylphenol(including isomers), 2-heptyl-4-octylphenol (including isomers),2-heptyl-4-phenylphenol (including isomers), 2-heptyl-4-cumylphenol(including isomers), 2,4,6-trimethylphenol, 2,6-dimethyl-4-ethylphenol,2,6-dimethyl-4-propylphenol (including isomers),2,6-dimethyl-4-butylphenol (including isomers),2,6-dimethyl-4-pentylphenol (including isomers),2,6-dimethyl-4-hexylphenol (including isomers),2,6-dimethyl-4-phenylphenol, 2,6-dimethyl-4-cumylphenol,2,4,6-triethylphenol, 2,6-diethyl-4-methylphenol,2,6-diethyl-4-propylphenol (including isomers),2,6-diethyl-4-butylphenol (including isomers),2,6-diethyl-4-pentylphenol (including isomers),2,6-diethyl-4-hexylphenol (including isomers),2,6-diethyl-4-phenylphenol (including isomers),2,6-diethyl-4-cumylphenol, 2,4,6-tripropylphenol (including isomers),2,6-dipropyl-4-ethylphenol (including isomers),2,6-dipropyl-4-methylphenol (including isomers),2,6-dipropyl-4-butylphenol (including isomers),2,6-dipropyl-4-pentylphenol (including isomers),2,6-dipropyl-4-hexylphenol (including isomers),2,6-dipropyl-4-phenylphenol (including isomers),2,6-dipropyl-4-cumylphenol (including isomers),2,4-dimethyl-6-ethylphenol, 2-methyl-4,6-diethylphenol,2-methyl-4-propyl-6-ethylphenol (including isomers),2-methyl-4-butyl-6-ethylphenol (including isomers),2-methyl-4-pentyl-6-ethylphenol (including isomers),2-methyl-4-hexyl-6-ethylphenol (including isomers),2-methyl-4-phenyl-6-ethylphenol (including isomers),2-methyl-4-cumyl-6-ethylphenol (including isomers),2,4-dimethyl-6-propylphenol (including isomers),2-methyl-4,6-dipropylphenol (including isomers),2-methyl-4-ethyl-6-propylphenol (including isomers),2-methyl-4-butyl-6-propylphenol (including isomers),2-methyl-4-pentyl-6-propylphenol (including isomers),2-methyl-4-hexyl-6-propylphenol (including isomers),2-methyl-4-phenyl-6-propylphenol (including isomers),2-methyl-4-cumyl-6-propylphenol (including isomers),2,4-dimethyl-6-butylphenol, 2-methyl-4,6-dibutylphenol (includingisomers), 2-methyl-4-propyl-6-butylphenol (including isomers),2-methyl-4-ethyl-6-butylphenol (including isomers),2-methyl-4-pentyl-6-butylphenol (including isomers),2-methyl-4-hexyl-6-butylphenol (including isomers),2-methyl-4-phenyl-6-butylphenol (including isomers),2-methyl-4-cumyl-6-butylphenol (including isomers),2,4-dimethyl-6-pentylphenol, 2-methyl-4,6-dipentylphenol,2-methyl-4-propyl-6-pentylphenol (including isomers),2-methyl-4-butyl-6-pentylphenol (including isomers),2-methyl-4-ethyl-6-pentylphenol (including isomers),2-methyl-4-hexyl-6-pentylphenol (including isomers),2-methyl-4-phenyl-6-pentylphenol (including isomers),2-methyl-4-cumyl-6-pentylphenol (including isomers),2,4-dimethyl-6-hexylphenol, 2-methyl-4,6-dihexylphenol,2-methyl-4-propyl-6-hexylphenol (including isomers),2-methyl-4-butyl-6-hexylphenol (including isomers),2-methyl-4-pentyl-6-hexylphenol (including isomers),2-methyl-4-ethyl-6-hexylphenol (including isomers),2-methyl-4-phenyl-6-hexylphenol (including isomers),2-methyl-4-cumyl-6-hexylphenol (including isomers),2-ethyl-4-methyl-6-propylphenol (including isomers),2,4-diethyl-6-propylphenol (including isomers), 2-ethyl-4,6-propylphenol(including isomers), 2-ethyl-4-butyl-6-propylphenol (including isomers),2-ethyl-4-pentyl-6-propylphenol (including isomers),2-ethyl-4-hexyl-6-propylphenol (including isomers),2-ethyl-4-heptyl-6-propylphenol (including isomers),2-ethyl-4-octyl-6-propylphenol (including isomers),2-ethyl-4-phenyl-6-propylphenol (including isomers),2-ethyl-4-cumyl-6-propylphenol (including isomers),2-ethyl-4-methyl-6-butylphenol (including isomers),2,4-diethyl-6-butylphenol (including isomers), 2-ethyl-4,6-butylphenol(including isomers), 2-ethyl-4-propyl-6-butylphenol (including isomers),2-ethyl-4-pentyl-6-butylphenol (including isomers),2-ethyl-4-hexyl-6-butylphenol (including isomers),2-ethyl-4-heptyl-6-butylphenol (including isomers),2-ethyl-4-octyl-6-butylphenol (including isomers),2-ethyl-4-phenyl-6-butylphenol (including isomers),2-ethyl-4-cumyl-6-butylphenol (including isomers),2-ethyl-4-methyl-6-pentylphenol (including isomers),2,4-diethyl-6-pentylphenol (including isomers), 2-ethyl-4,6-pentylphenol(including isomers), 2-ethyl-4-butyl-6-pentylphenol (including isomers),2-ethyl-4-propyl-6-pentylphenol (including isomers),2-ethyl-4-hexyl-6-pentylphenol (including isomers),2-ethyl-4-heptyl-6-pentylphenol (including isomers),2-ethyl-4-octyl-6-pentylphenol (including isomers),2-ethyl-4-phenyl-6-pentylphenol (including isomers),2-ethyl-4-cumyl-6-pentylphenol (including isomers),2-ethyl-4-methyl-6-hexylphenol (including isomers),2,4-diethyl-6-hexylphenol (including isomers), 2-ethyl-4,6-hexylphenol(including isomers), 2-ethyl-4-propyl-6-hexylphenol (including isomers),2-ethyl-4-pentyl-6-hexylphenol (including isomers),2-ethyl-4-butyl-6-hexylphenol (including isomers),2-ethyl-4-heptyl-6-hexylphenol (including isomers),2-ethyl-4-octyl-6-hexylphenol (including isomers),2-ethyl-4-phenyl-6-hexylphenol (including isomers),2-ethyl-4-cumyl-6-hexylphenol (including isomers),2-propyl-4-methyl-6-butylphenol (including isomers),2,4-dipropyl-6-butylphenol (including isomers), 2-propyl-4,6-butylphenol(including isomers), 2-propyl-4-ethyl-6-butylphenol (including isomers),2-propyl-4-pentyl-6-butylphenol (including isomers),2-propyl-4-hexyl-6-butylphenol (including isomers),2-propyl-4-heptyl-6-butylphenol (including isomers),2-propyl-4-octyl-6-butylphenol (including isomers),2-propyl-4-phenyl-6-butylphenol (including isomers) and2-propyl-4-cumyl-6-butylphenol (including isomers). One type of thesearomatic hydroxy compounds may be used or a plurality of types may beused in combination.

<Isocyanate Production Process>

In the present embodiment, isocyanates can be produced by using thecomposition containing the carbamic acid ester and the aromatic hydroxycompound as described above. The following provides an explanation of anisocyanate production process in the present embodiment.

In the isocyanate production process of the present embodiment, theisocyanates can be produced by transferring the composition containingthe carbamic acid ester and the aromatic hydroxy compound as describedabove to a reaction vessel where a thermal decomposition reaction of thecarbamic acid ester is carried out. This process is a process forproducing isocyanates comprising the following steps (1), (3), (4) and(5) or a process comprising the following steps (2), (3), (4) and (5):

step (1): reacting an amine compound and a carbonic acid ester so as toobtain a mixture containing a carbamic acid ester, an alcohol and acarbonic acid ester;

step (2): reacting an amine compound, an urea and an alcohol so as toobtain a mixture containing a carbamic acid ester, an alcohol and a ureacompound;

step (3): separating the alcohol and the carbonic acid ester or the ureacontained in the mixture by using the mixture of step (1) or step (2)and the aromatic hydroxyl compound so as to obtain a compositioncontaining the carbamic acid ester and an aromatic hydroxy compound;step (4): transferring the composition obtained in step (3) in a liquidstate to a step (5); and

step (5): producing the isocyanate using the composition transferred instep (4).

<Step (1)>

The following provides an explanation of a process for producingcarbamic acid ester by a reaction between the carbonic acid ester andthe amine compound in step (1).

A carbonic acid ester represented by the following formula (26) can beused for the carbonic acid ester:

(wherein R⁸ represents a linear or branched alkyl group having 1 to 8carbon atoms).

More preferable examples of R⁸ in formula (26) above may include linearor branched aliphatic hydrocarbon groups having 1 to 8 carbon atoms,while even more preferable examples may include linear or branched alkylgroups having 1 to 8 carbon atoms. Examples of such R⁸ may include alkylgroups in the form of aliphatic hydrocarbon groups in which the numberof carbon atoms constituting the group is a number selected from thegroup consisting of integers of 1 to 8, such as a methyl group, an ethylgroup, a propyl group (including isomers), a butyl group (includingisomers), a pentyl group (including isomers), a hexyl group (includingisomers), a heptyl group (including isomers) or an octyl group(including isomers). Examples of such dialkyl carbonates may includedimethyl carbonate, diethyl carbonate, dipropyl carbonate (includingisomers), dibutyl carbonate (including isomers), dipentyl carbonate(including isomers), dihexyl carbonate (including isomers), diheptylcarbonate (including isomers) and dioctyl carbonate (including isomers).In particular, dialkyl carbonates in which the number of carbon atomsconstituting the alkyl group is a number selected from the groupconsisting of integers of 4 to 6 are used preferably.

Although the known process can be used to produce the carbonic acidester, carbonic acid ester is preferably produced by reacting an organictin compound having a tin-oxygen-carbon bond with carbon dioxide.Namely, the carbonic acid ester can be produced by the following steps:

step (A): (carbonic acid ester formation step) reacting an organic tincompound having a tin-oxygen-carbon bond with carbon dioxide so as toobtain a reaction mixture containing carbonic acid ester; and

step (B): (carbonic acid ester separation step) separating the carbonicacid ester from the reaction mixture as well as obtaining a distillationresidue.

In addition, the following steps (C) and (D) may be carried out inaddition to these steps (A) and (B):

step (C): (organic tin compound regeneration step) reacting with thedistillation residue obtained in step (B) with an alcohol so as to forman organic tin compound having a tin-oxygen-carbon bond and a waterfollowed by removing the water from a reaction system; and

step (D): (recycling step) reusing the organic tin compound having thetin-oxygen-carbon bond obtained in step (C) as the organic tin compoundhaving the tin-oxygen-carbon bond in step (A).

Dialkyl tin compounds are preferably used for the organic tin compoundused in step (A). The term “dialkyl tin compound” refers to an organictin compound in which two alkyl groups are bonded to a single tin atom.

Examples of these dialkyl tin compounds may include compounds selectedfrom at least one type of compound selected from the group consisting ofdialkyl tin compounds represented by the following formula (27) andtetraalkyl distannoxane compounds represented by the following formula(28):

(wherein each of R¹³ and R¹⁴ independently represents a linear orbranched alkyl group having 1 to 12 carbon atoms,

Each of X¹ and X² independently represents at least one type ofsubstituent selected from the group consisting of an alkoxy group, anacyloxyl group and a halogen atom,

each of a and b independently represents an integer of 0 to 2, anda+b=2, and

each of c and d independently represents an integer of 0 to 2, andc+d=2);

(wherein each of R¹⁵, R¹⁶, R¹⁷ and R¹⁸ independently represents a linearor branched alkyl group having 1 to 12 carbon atoms,

X³ and X⁴ represent at least one type of substituent selected from thegroup consisting of an alkoxy group, an acyloxyl group and a halogenatom, and

each of e, f, g and h independently represents an integer of 0 to 2,e+f=2 and g+h=2).

Examples of R¹³ and R¹⁴ in the dialkyl tin catalyst represented byformula (27) above as well as examples of R¹⁵, R¹⁶, R¹⁷ and R¹⁸ in thetetraalkyl distannoxane compound represented by formula (28) above mayinclude alkyl groups in the form of aliphatic hydrocarbon groups inwhich the number of carbon atoms constituting the group is a numberselected from the group consisting of integers of 1 to 12, such as amethyl group, an ethyl group, a propyl group (including isomers), abutyl group (including isomers), a pentyl group (including isomers), ahexyl group (including isomers), a heptyl group (including isomers), anoctyl group (including isomers), a nonyl group (including isomers), adecyl group (including isomers) or a dodecyl group (including isomers).More preferable examples may include linear or branched alkyl groups inwhich the number of carbon atoms constituting the group is a numberselected from the group consisting of integers of 1 to 8, and althoughdialkyl tin compounds can be used in which the alkyl group is an alkylgroup in which the number of carbon atoms constituting the group isoutside the range indicated above, there are cases in which fluidity maybe poor or productivity may be impaired. Moreover, an n-butyl group orn-octyl group is more preferable in consideration of ease of acquisitionduring industrial production.

X¹ and X² of the dialkyl tin compound represented by formula (27) aboveand X³ and X⁴ of the tetraalkyl distannoxane compound represented byformula (28) above represent at least one type of substituent selectedfrom the group consisting of an alkoxy group, an acyloxyl group and ahalogen atom, and in the case the group is an alkoxy group and/or anacyloxy group, the number of carbon atoms constituting the group ispreferably a number selected from the group consisting of integers of 0to 12. Examples of such groups may include alkoxy groups composed of alinear or branched saturated alkyl group and an oxygen atom, such as amethoxy group, an ethoxy group, a propoxy group (including isomers), abutoxy group (including isomers), a pentyloxy group (including isomers),a hexyloxy group (including isomers), a heptyloxy group (includingisomers), an octyloxy group (including isomers), a nonyloxy group(including isomers) or a decyloxy group (including isomers); an acyloxygroups composed of a linear or branched saturated alkyl group, acarbonyl group and an oxygen atom, such as an acetoxy group, apropionyloxy group, a butyryloxy group, a valeryloxy group or alauroyloxy group; and halogen atoms such as a chloro group or bromogroup. More preferable examples may include alkoxy groups having 4 to 6carbon atoms in consideration of fluidity and solubility as well as useof the carbonic acid ester as a production catalyst.

Examples of dialkyl tin compounds represented by formula (27) mayinclude dialkyl-dialkoxy tins such as dimethyl-dimethoxy tin,dimethyl-diethoxy tin, dimethyl-dipropoxy tin (including isomers),dimethyl-dibutoxy tin (including isomers), dimethyl-dipentyloxy tin(including isomers), dimethyl-dihexyloxy tin (including isomers),dimethyl-diheptyloxy tin (including isomers), dimethyl-dioctyloxy tin(including isomers), dimethyl-dinonyloxy tin (including isomers),dimethyl-didecyloxy tin (including isomers), dibutyl-dimethoxy tin(including isomers), dibutyl-diethoxy tin (including isomers),dibutyl-dipropoxy tin (including isomers), dibutyl-dibutyloxy tin(including isomers), dibutyl-dipentyloxy tin (including isomers),dibutyl-dihexyloxy tin (including isomers), dibutyl-diheptyloxy tin(including isomers), dibutyl-dioctyloxy tin (including isomers),dibutyl-dinonyloxy tin (including isomers), dibutyl-didecyloxy tin(including isomers), dioctyl-dimethoxy tin (including isomers),dioctyl-diethoxy tin (including isomers), dioctyl-dipropoxy tin(including isomers), dioctyl-dibutyloxy tin (including isomers),dioctyl-dipentyloxy tin (including isomers), dioctyl-dihexyloxy tin(including isomers), dioctyl-diheptyloxy tin (including isomers),dioctyl-dioctyloxy tin (including isomers), dioctyl-dinonyloxy tin(including isomers) or dioctyl-didecyloxy tin (including isomers);dialkyl-diacyloxy tins such as dimethyl-diacetoxy tin,dimethyl-dipropionyloxy tin (including isomers), dimethyl-dibutyryloxytin (including isomers), dimethyl-valeryloxy tin (including isomers),dimethyl-dilauroyloxy tin (including isomers), dibutyl-diacetoxy tin(including isomers), dibutyl-dipropionyloxy tin (including isomers),dibutyl-dibutyryloxy tin (including isomers), dibutyl-divaleryloxy tin(including isomers), dibutyl-dilauroyloxy tin (including isomers),dioctyl-diacetoxy tin (including isomers), dioctyl-dipropionyloxy tin(including isomers), dioctyl-dibutyryloxy tin (including isomers),dioctyl-valeryloxy tin (including isomers) or dioctyl-dilauroyloxy tin(including isomers); and, dialkyl-dihalide tins such asdimethyl-dichloro tin, dimethyl-dibromo tin, dibutyl-dichloro tin(including isomers), dibutyl-dibromo tin (including isomers),dioctyl-dichloro tin (including isomers) or dioctyl-dibromo tin(including isomers).

Among these, dialkyl tin dialkoxides such as dimethyl-dimethoxy tin,dimethyl-diethoxy tin, dimethyl-dipropoxy tin (including isomers),dimethyl-dibutoxy tin (including isomers), dimethyl-dipentyloxy tin(including isomers), dimethyl-dihexyloxy tin (including isomers),dimethyl-diheptyloxy tin (including isomers), dimethyl-dioctyloxy tin(including isomers), dimethyl-dinonyloxy tin (including isomers),dimethyl-didecyloxy tin (including isomers), dibutyl-dimethoxy tin(including isomers), dibutyl-diethoxy tin (including isomers),dibutyl-dipropoxy tin (including isomers), dibutyl-dibutyloxy tin(including isomers), dibutyl-dipentyloxy tin (including isomers),dibutyl-dihexyloxy tin (including isomers), dibutyl-diheptyloxy tin(including isomers), dibutyl-dioctyloxy tin (including isomers),dibutyl-dinonyloxy tin (including isomers), dibutyl-didecyloxy tin(including isomers), dioctyl-dimethoxy tin (including isomers),dioctyl-diethoxy tin (including isomers), dioctyl-dipropoxy tin(including isomers), dioctyl-dibutyloxy tin (including isomers),dioctyl-dipentyloxy tin (including isomers), dioctyl-dihexyloxy tin(including isomers), dioctyl-diheptyloxy tin (including isomers),dioctyl-dioctyloxy tin (including isomers), dioctyl-dinonyloxy tin(including isomers) or dioctyl-didecyloxy tin (including isomers) arepreferable, dialkyl-dialkoxy tins such as dibutyl-dipropoxy tin(including isomers), dibutyl-dibutyryloxy tin (including isomers),dibutyl-dipentyloxy tin (including isomers), dibutyl-dihexyloxy tin(including isomers), dibutyl-diheptyloxy tin (including isomers),dioctyl-dipropoxy tin (including isomers), dioctyl-dibutoxy tin(including isomers), dioctyl-dipentyloxy tin (including isomers),dioctyl-dihexyloxy tin (including isomers) or dioctyl-diheptyloxy tin(including isomers) are more preferable, and dibutyl-dibutyloxy tin(including isomers), dibutyl-dipentyloxy tin (including isomers),dibutyl-dihexyloxy tin (including isomers), dibutyl-diheptyloxy tin(including isomers), dibutyl-dioctyloxy tin (including isomers),dioctyl-dibutyloxy tin (including isomers), dioctyl-dipentyloxy tin(including isomers), dioctyl-dihexyloxy tin (including isomers),dioctyl-diheptyloxy tin (including isomers) or dioctyl-dioctyloxy tin(including isomers) is even more preferable.

Although the dialkyl tin compound represented by the formula (27) has amonomer structure, this may be a polymer structure or associate.

Examples of the tetraalkyl dialkoxy distannoxane represented by theformula (28) may include 1,1,3,3-tetraalkyl-1,3-dialkoxy distannoxanessuch as 1,1,3,3-tetramethyl-1,3-dimethoxy distannoxane,1,1,3,3-tetramethyl-1,3-diethoxy distannoxane,1,1,3,3-tetramethyl-1,3-dipropoxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dibutoxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dipentyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dihexyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-diheptyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dioctyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dinonyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-didecyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dimethoxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-diethoxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dipropoxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dibutoxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dipentyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dihexyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-diheptyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dioctyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dinonyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-didecyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dimethoxy distannoxane (including isomers),1,1,3,3-tetraocyl-1,3-diethoxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dipropoxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dibutoxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dipentyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dihexyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-diheptyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dioctyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dinonyloxy distannoxane (including isomers) or1,1,3,3-tetraoctyl-1,3-didecyloxy distannoxane (including isomers);1,1,3,3-tetraalkyl-1,3-diacyloxy distannoxanes such as1,1,3,3-tetramethyl-1,3-diacetoxy distannoxane,1,1,3,3-tetramethyl-1,3-dipropionyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dibutyryloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-divaleryloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dilauroyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-diacetoxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dipropionyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dibutyryloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-divaleryloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dilauroyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-diacetoxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dipropionyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dibutyryloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-diyaleryloxy distannoxane (including isomers) or1,1,3,3-tetraoctyl-1,3-dilauroyloxy distannoxane (including isomers);and, 1,1,3,3-tetraalkyl-1,3-dihalide distannoxanes such as1,1,3,3-tetramethyl-1,3-dichloro distannoxane,1,1,3,3-tetramethyl-1,3-dibromo distannoxane,1,1,3,3-tetrabutyl-1,3-dichloro distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dibromo distannoxane (including isomers),1,1,3,3-tetraocyl-1,3-dichloro distannoxane (including isomers) or1,1,3,3-tetraocyl-1,3-dibromo distannoxane (including isomers).

Among these, 1,1,3,3-tetraalkyl-1,3-dialkoxy distannoxanes such as1,1,3,3-tetramethyl-1,3-dimethoxy distannoxane,1,1,3,3-tetramethyl-1,3-diethoxy distannoxane,1,1,3,3-tetramethyl-1,3-dipropoxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dibutoxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dipentyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dihexyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-diheptyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dioctyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-dinonyloxy distannoxane (including isomers),1,1,3,3-tetramethyl-1,3-didecyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dimethoxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-diethoxydistannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dipropoxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dibutoxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dipentyloxydistannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dihexyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-diheptyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dioctyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-dinonyloxy distannoxane (including isomers),1,1,3,3-tetrabutyl-1,3-didecyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dimethoxy distannoxane (including isomers),1,1,3,3-tetraocyl-1,3-diethoxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dipropoxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dibutoxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dipentyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dihexyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-diheptyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dioctyloxy distannoxane (including isomers),1,1,3,3-tetraoctyl-1,3-dinonyloxy distannoxane (including isomers) or1,1,3,3-tetraoctyl-1,3-didecyloxy distannoxane (including isomers) arepreferable, and 1,1,3,3-tetrabutyl-1,3-dibutoxy distannoxane (includingisomers), 1,1,3,3-tetrabutyl-1,3-dipentyloxy distannoxane (includingisomers), 1,1,3,3-tetrabutyl-1,3-dihexyloxy distannoxane (includingisomers), 1,1,3,3-tetrabutyl-1,3-diheptyloxydistannoxane (includingisomers), 1,1,3,3-tetrabutyl-1,3-dioctyloxy distannoxane (includingisomers), 1,1,3,3-tetraoctyl-1,3-dibutoxy distannoxane (includingisomers), 1,1,3,3-tetraoctyl-1,3-dipentyloxydistannoxane (includingisomers), 1,1,3,3-tetraoctyl-1,3-dihexyloxy distannoxane (includingisomers), 1,1,3,3-tetraoctyl-1,3-diheptyloxy distannoxane (includingisomers) or 1,1,3,3-tetraoctyl-1,3-dioctyloxy distannoxane (includingisomers) is more preferable.

Although the tetraalkyl dialkoxy distannoxane represented by formula(28) has a monomer structure, this may be a polymer structure orassociate.

In general, organic tin compounds easily take an associated structure,and although, for example, dialkyl tin dialkoxy tin is known to form adimer structure, and tetraalkyl dialkoxy distannoxanes are known to bepresent by forming a ladder structure in which two or three moleculesare associated, even in cases in which there are changes in thisassociated state, the representation of a compound in the form of amonomer structure is common for a person with ordinary skill in the art.

In addition, the previously indicated dialkyl tin alkoxide compound maybe used alone or two or more types may be used as a mixture.

A previously disclosed production process (such as that disclosed in WO2005/111049) can preferably be used as the process for producing thedialkyl tin compound. This process is a process for producing a dialkyltin compound from a dialkyl tin oxide and an alcohol.

Examples of alcohols used in the present embodiment may include alcoholssuch as methanol, ethanol, propanol (including isomers), butanol(including isomers), pentanol (including isomers), hexanol (includingisomers), heptanol (including isomers), octanol (including isomers),nonanol (including isomers) or decanol (including isomers), and analcohol is preferably used in which the number of carbon atomsconstituting the alcohol is a number selected from the group consistingof integers of 1 to 12.

Dialkyl tin oxides represented by the following formula (29) are usedfor the dialkyl tin oxide used in the alkyl tin alkoxide synthesisprocess:

(wherein each of R¹⁹ and R²⁰ independently represents a linear orbranched alkyl group having 1 to 12 carbon atoms).

Examples of R¹⁹ and R²⁰ may include alkyl groups in the form ofaliphatic hydrocarbon groups having 1 to 12 carbon atoms, such as amethyl group, an ethyl group, a propyl group (including isomers), abutyl group (including isomers), a pentyl group (including isomers), ahexyl group (including isomers), a heptyl group (including isomers), anoctyl group (including isomers), a nonyl group (including isomers), adecyl group (including isomers), an undecyl group (including isomers) ora dodecyl group (including isomers). More preferable examples mayinclude linear or branched saturated alkyl groups having 1 to 8 carbonatoms. Even more preferable examples may include a n-butyl group and an-octyl group.

A tetraalkyl dialkoxy distannoxane and/or dialkyl tin dialkoxide isobtained by a dehydration reaction of the alcohol and the dialkyl tinoxide while removing the water formed from the system. The temperatureat which the reaction is carried out is, for example, within the rangeof from 80 to 180° C., and in order to distill off the water formed fromthe system, although varying according to the reaction pressure, atemperature of from 100 to 180° C. is preferable. Although a hightemperature is preferable for the reaction temperature to accelerate thereaction rate, since undesirable reactions such as decomposition alsooccur at high temperatures thereby decreasing yield, the reactiontemperature is more preferably within the range of from 100 to 160° C.The reaction pressure is a pressure that allows water formed to beremoved from the system, and the reaction is carried out at a pressureof from 20 to 1×10⁶ Pa, although varying according to the reactiontemperature. There are no particular limitations on the reaction time ofthe dehydration reaction, and is generally from 0.001 to 50 hours,preferably from 0.01 to 10 hours and more preferably from 0.1 to 2hours. The reaction may be terminated once the desired alkyl tinalkoxide composition has been obtained. Progression of the reaction isalso determined by measuring the amount of water extracted outside thesystem, and can also be determined by a method using ¹¹⁹Sn-NMR bysampling the reaction liquid. In order to produce the mixture of thepresent embodiment in step 1, the reaction is terminated afterconfirming the obtaining of a composition in which the molar ratio oftetraalkyl dialkoxy distannoxane and dialkyl tin dialkoxide contained inthe alkyl tin alkoxide composition obtained in the above reaction, whenexpressed as the combined molar ratio of both, is within the range offrom 0:100 to 80:20 and more preferably within the range of from 10:90to 70:30. The alcohol used may be used while still present in thereaction system, and the alcohol may also be used by distilling off thealcohol depending on the case. Since there is the advantage of beingable to reduce the size of the reaction vessels of the other steps, itis preferable to remove as much of the alcohol as possible. Removal byknown distillation is preferable for the removal method, and knowndistillation equipment can be used for the distiller used fordistillation. A thin film distillation apparatus is preferably used forthe distillation apparatus since the alcohol can be removed in a shortperiod of time. There are no particular limitations on the type ofreaction vessel of the dehydration reaction, and the known tank type orthe column type reaction vessel can be used. A low boiling pointreaction mixture containing water is extracted in gaseous form from thereaction vessel by distillation, while a high boiling point reactionmixture containing a produced alkyl tin alkoxide or alkyl tin alkoxidemixture is extracted in the form of a liquid from the lower portion ofthe reaction vessel. Various known methods are used for such a reactionvessel, examples of which may include types using reaction vesselscontaining a stirring tank, a multistage stirring tank, a distillationcolumn, a multistage distillation column, a multitubular reactor, acontinuous multistage distillation column, a packed column, a thin filmdistillation apparatus, a reactor provided with a support inside, aforced circulation reactor, a falling film evaporator, a falling dropevaporator, a trickle flow reactor or a bubble column, and types usingcombinations thereof. Methods using a columnar reactor are preferablefrom the viewpoint of efficiently shifting the equilibrium to theproducts side, while a structure having a large gas-liquid contact areais preferable for being able to rapidly transfer the water formed to thegaseous phase. Although continuous methods using a multitubular reactor,a multistage distillation column or a packed column packed with apacking can also be used, since the dialkyl tin oxide used in this stepis generally a solid, it is preferable to employ a method in which thereaction is first carried out in a tank-type reaction vessel followed byincreasing the content of dialkyl tin dialkoxide in a column-typereaction vessel. Although known materials may be used for the materialsof the reaction vessel and lines provided they do not have a detrimentaleffect, materials such as SUS304, SUS316 or SUS316L are inexpensive andcan be used preferably. Known process apparatuses such as a flow meter,a thermometer and other measuring instruments or a reboiler, a pump or acondenser and the like may be added as necessary, the known method suchas steam or a heater may be used for heating, and the known method suchas air cooling, cooling water or brine can be used for cooling.

Step (A) is a step for producing the carbonic acid esters by reactingthe dialkyl tin compounds produced according to the process describedabove with gaseous carbon dioxide. A previously disclosed carbonic acidester production process (such as that disclosed in WO 03/055840 or WO04/014840) is preferably used in this step.

The alkyl tin compound supplied to this step may be supplied from analkyl tin alkoxide synthesis step at the start of production, or from adialkyl tin compound production step of step (C) to be described laterduring continuous production.

In this step, the above-mentioned dialkyl tin alkoxide and gaseouscarbon dioxide are absorbed and undergo a chemical reaction to obtain amixture containing a carbon dioxide-bonded form of the dialkyl tinalkoxide.

During this chemical reaction, the dialkyl tin alkoxide is reacted inliquid form. The dialkyl tin alkoxide is preferably put into liquid formby heating. In addition, it may also be put into liquid form by asolvent and the like. Although varying according to the reactiontemperature, the reaction pressure is preferably within the range offrom a normal pressure to 1 MPa, more preferably within the range offrom the normal pressure to 0.6 MPa. Although varying according to thereaction pressure, the reaction temperature is preferably within therange of from −40 to 80° C., and in consideration of fluidity duringtransfer, more preferably from 0 to 80° C. and even more preferablywithin the range of from a normal temperature (e.g., 20° C.) to 80° C.The reaction time may be within the range of from several seconds to 100hours, and in consideration of productivity and the like, is preferablyfrom several minutes to 10 hours. A known tank type reaction vessel or acolumn type reaction vessel can be used for the reaction vessel. Inaddition, a plurality of reaction vessels may be used in combination.Since the reaction is a reaction between carbon dioxide gas (gas) and analkyl tin alkoxide composition (liquid), in order to carry out thereaction efficiently, it is preferable to increase the contact surfacearea between the gas and liquid by increasing the gas-liquid interface.Known findings can be used for the method for reacting while increasingthe gas-liquid interface in this manner, and examples of preferablemethods thereof may include increasing the stirring speed or generatingbubbles in the liquid in the case of a tank type reaction vessel, andusing a packed column or using a plate column in the case of a columntype reaction vessel. Examples of such column type reaction vessels mayinclude plate column types using a tray such as a bubble tray, a porousplate tray, a valve tray or a counter-current tray, and packed columntypes packed with various types of packing materials such as a raschigring, a lessing ring, a pole ring, a Berl saddle, an Interlock saddle, aDixon packing, a McMahon packing, Helipack, a Sulzer packing orMellapak. Although known materials may be used for the materials of thereaction vessel and lines provided they do not have a detrimentaleffect, materials such as SUS304, SUS316 or SUS316L are inexpensive andcan be used preferably. Known process apparatuses such as a flow meter,a thermometer and other measuring instruments or a reboiler, pump or acondenser and the like may be added as necessary, the known method suchas steam or a heater may be used for heating, and the known method suchas air cooling, cooling water or brine can be used for cooling. Sincethe reaction is generally an exothermic reaction, the reaction vesselmay be cooled or it may be cooled by dissipation of heat there from.Alternatively, the reaction vessel may also be heated if the purpose iscombining with a carbonic acid esterification reaction. A known methodsuch as a method using a heat jacket or a method using an internal coilcan be used to heat and cool the reaction vessel. The carbon dioxide gasand alkyl tin alkoxide composition supplied to the reaction vessel maybe supplied separately to the reaction vessel or they may be mixed priorto supplying to the reaction vessel. These components may also besupplied from a plurality of locations in the reaction vessel.Completion of the reaction can be determined by, for example, ¹¹⁹Sn-NMRanalysis.

Next, the reaction liquid containing carbonic acid ester is obtainedfrom the carbon dioxide associate of dialkyl tin alkoxide obtained inthe above manner according to the method described below.

Although the reaction temperature is within the range of from 110 to200° C., and a high temperature is preferable for the reactiontemperature in order to accelerate the reaction rate, since undesirablereactions such as decomposition also occur at high temperatures therebydecreasing yield, the reaction temperature is more preferably within therange of from 120 to 180° C., the reaction time is preferably within therange of from 0.1 to 10 hours, and the reaction pressure is from 1.5 to20 MPa and preferably from 2.0 to 10 MPa. The reaction is terminatedafter the desired carbonic acid ester has formed in the reaction vessel.Progression of the reaction can be confirmed by, for example, samplingthe reaction liquid in the reaction vessel, and analyzing the carbonicacid ester formed by a method such as ¹H-NMR or gas chromatography. Forexample, the reaction may be terminated after the carbonic acid esterhas been formed at a molar ratio of 10% or more of the dialkyl tinalkoxide and/or carbon dioxide associate of the dialkyl tin alkoxidecontained in the dialkyl tin alkoxide and/or carbon dioxide associate ofthe dialkyl tin alkoxide, and in the case of desiring to increase theyield of the carbonic acid ester, the reaction may be terminated afterallowing to continue until the value reaches 90% or more. A knownreaction vessel can be used for the reaction vessel, and a column typereaction vessel or a tank type reaction vessel can be used preferably.Although known materials may be used for the materials of the reactionvessel and lines provided they do not have a detrimental effect,materials such as SUS304, SUS316 or SUS316L are inexpensive and can beused preferably. Known process apparatuses such as a flow meter, athermometer and other measuring instruments or a reboiler, a pump or acondenser and the like may be added as necessary, a known method such assteam or a heater may be used for heating, and a known method such asair cooling, cooling water or brine can be used for cooling.

Step (B) in the present embodiment is a step for obtaining adistillation residue from the reaction liquid containing carbonic acidester obtained in step (A) above by separating the carbonic acid ester.A known method or apparatus can be preferably used for the separationmethod, and a preferable method is distillation.

Carbonic acid ester and distillation residue are obtained by batch,semi-batch or continuous distillation of the reaction liquid transferredfrom step (A) above. A preferable example of the distillation method mayinclude supplying the reaction liquid to a distiller, separating thecarbonic acid ester in the form of a gaseous phase component from a topof the distiller outside the system, and extracting the distillationresidue in the form of a liquid component from the bottom of thedistiller. Although varying according to the boiling point and pressureof the carbonic acid ester, the temperature in this step is within therange of from a normal temperature (e.g., 20° C.) to 200° C., and sincethere are cases in which denaturation of tin compounds in thedistillation residue may occur or the amount of carbonic acid ester maydecrease due to a reverse reaction at high temperatures, the reactiontemperature is preferably within the range of from the normaltemperature (e.g. 20° C.) to 150° C. Although varying according to thetype of carbonic acid ester and temperature at which the reaction iscarried out, the reaction is generally carried out at normal pressure toreduced pressure conditions, and in consideration of productivity, thepressure is more preferably within the range of from 100 Pa to 80 KPaand most preferably within the range of from 100 Pa to 50 KPa. Thereaction can be carried out a reaction time within the range of from0.01 to 10 hours, and since there are cases in which tin compoundscontained in the reaction liquid are denatured and cases in which theamount of carbonic acid ester decreases due to a reverse reaction whenthe reaction is carried out for a long period of time at hightemperatures, the reaction time is preferably within the range of from0.01 to 0.5 hours and most preferably within the range of from 0.01 to0.3 hours. A known distiller can be used for the distiller, a columntype distiller or a tank type distiller can be used preferably, or aplurality of types can be used in combination. More preferable examplesof the distillers may include a thin film distillation apparatus and athin film distiller, and a thin film distillation apparatus providedwith a distillation column or a thin film distiller is most preferable.Although known materials may be used for the materials of the reactionvessel and lines provided they do not have a detrimental effect,materials such as SUS304, SUS316 or SUS316L are inexpensive and can beused preferably. Known process apparatuses such as a flow meter, athermometer and other measuring instruments or a reboiler, a pump or acondenser and the like may be added as necessary, a known method such assteam or a heater may be used for heating, and a known method such asair cooling, cooling water or brine can be used for cooling.

Although the above has indicated a production example of the carbonicacid ester using the dialkyl tin compound, the following steps (C) and(D) can be carried out in addition to the above-mentioned steps (A) and(B).

Step (C) is a step for regenerating a dialkyl tin compound by reactingthe distillation residue obtained in step (B) with an alcohol.

Examples of alcohols used in this step may include alcohols such asmethanol, ethanol, propanol (including isomers), butanol (includingisomers), pentanol (including isomers), hexanol (including isomers),heptanol (including isomers), octanol (including isomers), nonanol(including isomers) or decanol (including isomers), and although analcohol is preferably used in which the number of carbon atomsconstituting the alcohol is a number selected from the group consistingof integers of 1 to 12, more preferably an alcohol is used that is thesame alcohol as the alcohol used in the alkyl tin alkoxide synthesisstep above.

The conditions of the dehydration reaction are preferably the same asthe conditions of the above-mentioned alkyl tin alkoxide synthesis step.The reaction may be terminated once the desired alkyl tin alkoxidecomposition has been obtained. Progression of the reaction is alsodetermined by measuring the amount of water extracted outside thesystem, and can also be determined by a method using ¹¹⁹Sn-NMR bysampling the reaction liquid. In order to produce the mixture of thepresent embodiment in step 1, the reaction is terminated afterconfirming the obtaining of a composition in which the molar ratio oftetraalkyl dialkoxy distannoxane and dialkyl tin dialkoxide contained inthe alkyl tin alkoxide composition obtained in the above reaction, whenexpressed as the combined molar ratio of both, is within the range offrom 0:100 to 80:20 and more preferably within the range of from 10:90to 70:30. The alcohol used may be used while still present in thereaction system, and the alcohol may also be used by distilling off thealcohol depending on the case. Since there is the advantage of beingable to reduce the size of the reaction vessels of the other steps, itis preferable to remove as much of the alcohol as possible. Removal byknown distillation is preferable for the removal method, and knowndistillation equipment can be used for the distiller used fordistillation. A thin film distillation apparatus is preferably used forthe distillation apparatus since the alcohol can be removed in a shortperiod of time. Differing from the alkyl tin alkoxide synthesis step,since dialkyl tin oxide normally in a solid state is not used in thisstep, there are few restrictions on the reaction vessel. Namely, thereare no particular limitations on the type of reaction vessel of thedehydration reaction, and a known tank type or a column type reactionvessel can be used. A low boiling point reaction mixture containingwater is extracted in gaseous form from the reaction vessel bydistillation, while a high boiling point reaction mixture containing aproduced alkyl tin alkoxide or alkyl tin alkoxide mixture is extractedin the form of a liquid from the lower portion of the reaction vessel.Various known methods are used for such a reaction vessel, examples ofwhich may include types using reaction vessels containing a stirringtank, a multistage stirring tank, a distillation column, a multistagedistillation column, a multitubular reactor, a continuous multistagedistillation column, a packed column, a thin film evaporator, a reactorprovided with a support inside, a forced circulation reactor, a fallingfilm evaporator, a falling drop evaporator, a trickle flow reactor or abubble column, and types using combinations thereof. Methods using acolumnar reactor are preferable from the viewpoint of efficientlyshifting the equilibrium to the products side, while a structure havinga large gas-liquid contact area is preferable for being able to rapidlytransfer the water formed to the gaseous phase. Continuous methods usinga multitubular reactor, a multistage distillation column or a packedcolumn packed with a packing are particularly preferable. Although knownmaterials may be used for the materials of the reaction vessel and linesprovided they do not have a detrimental effect, materials such asSUS304, SUS316 or SUS316L are inexpensive and can be used preferably.Known process apparatuses such as a flow meter, a thermometer and othermeasuring instruments or a reboiler, a pump or a condenser and the likemay be added as necessary, a known method such as steam or a heater maybe used for heating, and a known method such as air cooling, coolingwater or brine can be used for cooling.

A dialkyl tin compound produced in step (C) above is reused as thedialkyl tin compound used in step (A) as a result of carrying out thefollowing step (D).

On the other hand, the amine compounds represented by the followingformula (30) are preferably used for the amine compounds used in step(1).

(wherein R⁷ represents a group selected from the group consisting of analiphatic group having 1 to 20 carbon atoms and an aromatic group having6 to 20 carbon atoms, the above groups containing an atom selected fromcarbon and oxygen atoms, and having a valence equal to n, and

n represents an integer of 2 to 10).

In formula (30) above, a polyamine in which n is 2 or more is usedpreferably, and a diamine compound in which n is 2 is used morepreferably.

In formula (30) above, R⁷ preferably represents a group previouslyexplained.

Examples of such polyamine compounds may include aliphatic diamines suchas hexamethylene diamine, 4,4′-methylenebis(cyclohexylamine) (includingisomers), cyclohexane diamine (including isomers) or3-aminomethyl-3,5,5-trimethylcyclohexyl amine (including isomers); andaromatic diamines such as phenylene diamine (including isomers), toluenediamine (including isomers) or 4,4′-methylene dianiline. Among these,aliphatic diamines such as hexamethylene diamine,4,4′-methylenebis(cyclohexylamine) (including isomers), cyclohexanediamine (including isomers) or 3-aminomethyl-3,5,5-trimethylcyclohexylamine (including isomers) are used preferably, hexamethylene diamine,4,4′-methylenebis(cyclohexylamine) and3-aminomethyl-3,5,5-trimethylcyclohexyl amine are used more preferably.

Reaction conditions under which the reaction of step (1) is carried outvary according to the reacted compounds, and although dialkyl carbonateis preferably in excess with respect to the amino groups of the aminecompound to accelerate the reaction rate and complete the reactionquickly at a stoichiometric ratio of the dialkyl carbonate to aminogroups of the amine compound within a range of from 2 to 1000 times, therange is preferably from 2 to 100 times, and more preferably from 2.5 to30 times in consideration of the size of the reaction vessel. Thereaction temperature is generally within the range of from a normaltemperature (20° C.) to 300° C., and although higher temperatures arepreferable in order to accelerate the reaction rate, since undesirablereactions may conversely occur at high temperatures, the reactiontemperature is preferably within the range of from 50 to 150° C. A knowncooling apparatus or heating apparatus may be installed in the reactionvessel to maintain a constant reaction temperature. In addition,although varying according to the types of compounds used and reactiontemperature, the reaction pressure may be a decreased pressure, a normalpressure or an increased pressure, and the reaction is generally carriedout at a pressure within the range of from 20 to 1×10⁶ Pa. There are noparticular limitations on the reaction time (residence time in the caseof a continuous method), and is generally from 0.001 to 50 hours,preferably from 0.01 to 10 hours and more preferably from 0.1 to 5hours. In addition, the reaction can also be terminated by confirmingthat a desired amount of alkyl carbamate has been formed by, forexample, liquid chromatography after sampling the reaction liquid. Inthe present embodiment, a catalyst can be used as necessary, andexamples of catalysts that can be used may include organic metalcompounds and inorganic metal compounds of tin, lead, copper ortitanium, and basic catalysts such as alkylates of alkaline metals oralkaline earth metals in the form of methylates, ethylates and butyrates(including isomers) of lithium, sodium, potassium, calcium or barium.

Although the use of a reaction solvent is not necessarily required inthe present embodiment, a suitable inert solvent is preferably used as areaction solvent for the purpose of facilitating the reaction procedure,examples of which may include alkanes such as hexane (includingisomers), heptane (including isomers), octane (including isomers),nonane (including isomers) or decane (including isomers); aromatichydrocarbons and alkyl-substituted aromatic hydrocarbons such asbenzene, toluene, xylene (including isomers), ethyl benzene, diisopropylbenzene (including isomers), dibutyl benzene (including isomers) ornaphthalene; aromatic compounds substituted with a halogen or nitrogroup such as chlorobenzene, dichlorobenzene (including isomers),bromobenzene, dibromobenzene (including isomers), chloronaphthalene,bromonaphthalene, nitrobenzene or nitronaphthalene; polycyclichydrocarbon compounds such as diphenyl, substituted diphenyl, diphenylmethane, terphenyl, anthracene or dibenzyl toluene (including isomers);aliphatic hydrocarbons such as cyclohexane, cyclopentane, cyclooctane orethylcyclohexane; ketones such as methyl ethyl ketone or acetophenone;esters such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalateor benzylbutyl phthalate; ethers and thioethers such as diphenyl etheror diphenyl sulfide; and sulfoxides such as dimethylsulfoxide ordiphenylsulfoxide. These solvents can be used alone or two or more typescan be used as a mixture. In addition, the dialkyl carbonate used inexcess with respect to amino groups of the amine compound is alsopreferably used as a solvent in the reaction.

A known tank type reaction vessel, a column type reaction vessel or adistillation column can be used for the reaction vessel, and althoughknown materials may be used for the reaction vessel and lines providedthey do not have a detrimental effect on the starting substances orreactants, SUS304, SUS316 or SUS316L and the like can be used preferablysince they are inexpensive.

According to step (1), the reaction mixture is obtained containingcarbamic acid ester, an excess of carbonic acid ester, and alcoholformed as a by-product of the reaction. The alcohol in the mixture is analcohol having an alkyl group derived from the carbonic acid ester usedin step (1).

<Step (2)>

The following provides an explanation of a process for producing acarbamic acid ester by a reaction between urea, an alcohol and an aminecompound of step (2).

Alcohols represented by the following formula (31) can be used for thealcohol.

R⁹—OH  (31)

(wherein R⁹ represents a linear or branched alkyl group having 1 to 10carbon atoms).

Examples of R⁹ in formula (31) above may include a methyl group, anethyl group, a propyl group (including isomers), a butyl group(including isomers), a pentyl group (including isomers), a hexyl group(including isomers), a heptyl group (including isomers), an octyl group(including isomers), a nonyl group (including isomers) and a decyl group(including isomers).

A previously described amine compound can be used for the aminecompound.

Although reaction conditions vary according to the reacted compounds,the stoichiometric ratio of the amount of alcohol to the amino groups ofthe amine compound used is within the range of from 1 to 500 times.Although it is preferable to use an excess amount of alcohol sincecomplex substituted urea compounds are formed easily if the amount ofalcohol used is less than 1 times the amino groups of the aminecompound, in consideration of the size of the reaction vessel, theamount of alcohol used is preferably within the range of from 1 to 100times and more preferably within the range of from 5 to 50 times. Thestoichiometric ratio of the amount of urea to the amino groups of thepolyamine compound is within the range of from 0.5 to 3 times. Althoughit is preferable to use an excess amount of urea since complexsubstituted urea compounds are formed easily if the amount of alcoholused is less than 0.5 times the amino groups of the amine compound,since complex substituted urea compounds form easily or unreacted urearemains even in cases of using an excess amount of urea, the amount ofurea used is preferably within the range of from 0.8 to 2 times. Thereaction temperature is preferably within the range of from 150 to 280°C. Since the alcohol and the amine compound, urea and by-product ammoniabond strongly at temperatures lower than 150° C., the reaction slows orhardly occurs at all, or complex substituted urea compounds increase,thereby making this undesirable. On the other hand, the urea decomposes,the alcohol is dehydrogenated and denatured, or decomposition,denaturation and so forth of the product in the form of polycarbamicacid ester occurs easily at temperatures higher than 280° C., therebymaking this undesirable. In this sense, the reaction temperature is morepreferably within the range of from 180 to 260° C. and even morepreferably within the range of from 200 to 250° C.

Since the reaction is an equilibrium reaction and the reaction is biasedtowards the reactants side, it is preferable to carry out the reactionwhile removing the by-product ammonia outside the system. Examples ofmethods thereof may include reactive distillation, use of an inert gas,membrane separation and adsorptive separation. For example, reactivedistillation refers to a method for separating ammonia continuouslyformed as a by-product during the reaction by distillation in the formof a gas. This can be carried out in the presence of a solvent or whileboiling a hydroxy compound in order to increase the distillationefficiency of the ammonia. In addition, a method using an inert gasrefers to a method for separating ammonia continuously formed as aby-product during the reaction from the reaction system in the form of agas along with the inert gas. Examples of inert gases used may includenitrogen, helium, argon, carbon dioxide, methane, ethane and propane,these may be used alone or as a mixture, and a method in which the inertgas is introduced into the reaction system is preferable. Examples ofadsorbents used in methods using adsorptive separation may includeadsorbents able to be used under the temperature conditions at which thereaction is carried out, such as silica, alumina, various types ofzeolite or diatomaceous earth. These methods for removing ammoniaoutside the system may be carried out alone or a plurality of types maybe carried out in combination.

A catalyst can be used in the reaction for the purpose of increasing thereaction rate. Examples of catalysts that are used preferably mayinclude basic catalysts such as methylates, ethylates or butyrates(including isomers) of lithium, sodium, potassium, calcium or barium,rare earth elements, antimony or bismuth alone or oxides, sulfides andsalts thereof, boron alone or boron compounds, metals of the copperfamily, zinc family, aluminum family, carbon family and titanium familyin the periodic table as well as metal oxides and sulfides thereof, andcarbides and nitrides of elements of the carbon family excluding carbon,titanium family, vanadium family and chromium family in the periodictable. Although there are no particular limitations on the amount ofcatalyst used in the case of using a catalyst, a catalyst can be usedwithin the range of a stoichiometric ratio of from 0.0001 to 100 timesthe amino groups of the amine compound.

Although the reaction pressure varies according to the composition ofthe reaction system, reaction temperature, ammonia removal method,reaction apparatus and the like, generally the reaction is preferablycarried out within the range of from 0.01 to 10 MPa, and preferablywithin the range of from 0.1 to 5 MPa in consideration of ease ofindustrial application. Although varying according to the composition ofthe reaction system, reaction temperature, ammonia removal method,reaction apparatus and reaction pressure and the like, the reaction timeis generally from 0.01 to 100 hours.

Although the use of a reaction solvent is not necessarily required inthe present embodiment, a suitable inert solvent is preferably used as areaction solvent for the purpose of facilitating the reaction procedure,examples of which may include alkanes such as pentane (includingisomers), hexane (including isomers), heptane (including isomers),octane (including isomers), nonane (including isomers) or decane(including isomers); aromatic hydrocarbons and alkyl-substitutedaromatic hydrocarbons such as benzene, toluene, xylene (includingisomers), ethyl benzene, diisopropyl benzene (including isomers),dibutyl benzene (including isomers) or naphthalene; nitrile compoundssuch as acetonitrile or benzonitrile; alcohols such as methanol,ethanol, propanol (including isomers), butanol (including isomers),pentanol (including isomers), hexanol (including isomers), heptanol(including isomers), octanol (including isomers) or nonanol (includingisomers); aromatic compounds substituted with a halogen or nitro groupsuch as chlorobenzene, dichlorobenzene (including isomers),bromobenzene, dibromobenzene (including isomers), chloronaphthalene,bromonaphthalene, nitrobenzene or nitronaphthalene; polycyclichydrocarbon compounds such as diphenyl, substituted diphenyl, diphenylmethane, terphenyl, anthracene or dibenzyl toluene (including isomers);aromatic hydroxy compounds such as phenol, methyl phenol (includingisomers), ethyl phenol (including isomers), butyl phenol (includingisomers), pentyl phenol (including isomers), dimethyl phenol (includingisomers), diethyl phenol (including isomers), dibutyl phenol (includingisomers) or dipentyl phenol (including isomers); aliphatic hydrocarbonssuch as cyclohexane, cyclopentane, cyclooctane or ethylcyclohexane;alicyclic alcohols such as cyclohexanol, cyclopentanol or cyclooctanol;ketones such as methyl ethyl ketone or acetophenone; esters such asdibutyl phthalate, dihexyl phthalate, dioctyl phthalate or benzylbutylphthalate; ethers and thioethers such as tetrahydrofuran, 1,4-dioxane,1,2-dimethoxyethane, diphenyl ether or diphenyl sulfide; ketonecompounds such as acetone or methyl ethyl ketone; ester compounds suchas ethyl acetate or ethyl benzoate; and sulfoxides such asdimethylsulfoxide or diphenylsulfoxide. Moreover, additional examplesmay include halogenated aromatic hydrocarbon compounds such aschlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene,chlorotoluene, chloronaphthalene or bromonaphthalene, and halogenatedaliphatic hydrocarbon compounds or halogenated alicyclic hydrocarboncompounds such as chlorohexane, chlorocyclohexane,trichlorofluoroethane, methylene chloride or carbon tetrachloride.

There are no particular limitations on the reaction apparatus used whencarrying out this reaction, and the known reaction vessel can be used.For example, conventionally known reaction vessels can be suitablycombined, such as a stirring tank, a pressurized stirring tank, adepressurized stirring tank, a column type reaction vessel, adistillation column, a packed column or a thin film distiller. There areno particular limitations on the material of the reaction vessel, andknown materials can be used, examples of which may include glass,stainless steel, carbon steel, Hastelloy, glass-lined base materials andTeflon (registered trademark) coated materials.

According to step (2), the mixture is obtained containing carbamic acidester, urea and alcohol.

<Step (3)>

Step (3) is a step that uses the mixture of step (1) or step (2) and anaromatic hydroxy compound to produce a composition containing carbamicacid ester and an aromatic hydroxy compound by separating the alcoholand carbonic acid ester or urea contained in the mixture.

The following provides an explanation of step (3).

Step (3) is preferably a step for obtaining a composition containing acarbamic acid ester and an aromatic hydroxy compound by separating analcohol and a carbonic acid ester or urea from a mixture of the mixtureof step (1) or step (2) and an aromatic hydroxy compound. Althoughseveral methods can be considered as methods for carrying out this step(3), in one aspect thereof, this step is carried out in a distillationapparatus, the mixture of step (1) or step (2) is supplied to adistillation apparatus as a mixture with an aromatic hydroxy compound,alcohol and carbonic acid ester or urea is recovered from a top of thecolumn, and the composition containing carbamic acid ester and aromatichydroxy compound is obtained from a bottom of the column.

In addition, in another aspect thereof, a mixture obtained by separatingall or a portion of the alcohol and/or a portion of the carbonic acidester or urea from the mixture of step (1) or step (2) is mixed with anaromatic hydroxy compound, and the carbonic acid ester or urea isseparated from the mixture. Namely, step (3) is carried out in adistillation apparatus, and is carried out with a process comprising thefollowing steps (3-1) and (3-2):

step (3-1): supplying the mixture of step (1) or step (2) to adistillation apparatus, an alcohol and/or a carbonic acid ester or anurea being recovered from a top of the column, and a mixture containingthe carbamic acid ester, the alcohol and/or the carbonic acid ester orthe urea being recovered from a bottom of the column;

step (3-2): supplying the mixture of step (3-1) to the distillationapparatus as a mixture with an aromatic hydroxy compound, the alcoholand/or the carbonic acid ester or the urea being recovered from a top ofthe column, and the composition containing the carbamic acid ester andthe aromatic hydroxy compound being recovered from the bottom of thecolumn.

The composition containing the mixture of carbamic acid ester andaromatic hydroxy compound can also be obtained by a method in whichcarbamic acid ester is obtained by distillative separation of carbonicacid ester and alcohol or the urea and alcohol are separated from areaction liquid obtained by producing a carbamic acid ester, followed bymixing with the mixture of the carbamic acid ester and aromatic hydroxycompound. However, in this method, during distillative separation, forexample, thermal denaturation of carbamic acid ester occurs easily as aresult of dimerization, oligomerization and the like due to theoccurrence of decarboxylation reactions between ester groups of thecarbamic acid ester as indicated in formula (2) above, which not onlycauses a decrease in the yield of carbamic acid ester, but also resultsin the problem of polymeric deposits accumulating in the reaction vesselwhere the distillative separation is carried out, thereby impairinglong-term operation. As a result of conducting extensive studies toresolve this problem, the inventors of the present invention found thatthe carbamic acid ester thermal denaturation reaction as described abovecan be inhibited by carrying out distillative separation of the carbonicacid ester and the alcohol or the urea and the alcohol from a reactionliquid obtained by producing carbamic acid ester in the presence of thepreviously described aromatic hydroxy compound, and recovering as amixture of carbamic acid ester and aromatic hydroxy compound, therebysolving the above problem. Although the mechanism by which thermaldenaturation of carbamic acid ester is inhibited is not clear, theinventors of the present invention presumed that, for example, the estergroups of the carbamic acid ester form hydrogen bonds with the aromatichydroxy compound, thereby inhibiting ester groups of the carbamic acidester from approaching each other due to the presence of the hydrogenbonds, which in turn inhibits the decarboxylation reaction between estergroups of the carbamic acid ester.

Although the amount of aromatic hydroxy compound used when carrying outthe distillative separation is such that the molar ratio of the numberof mole of ester groups of the carbamic acid ester contained in thereaction liquid and the number of mole of aromatic hydroxy compound iswithin the range of from 1:0.1 to 1:500, as previously stated, it ispreferable to use a large amount of the aromatic hydroxy compound inorder to inhibit thermal denaturation of the carbamic acid estercontained in the reaction liquid. However, in consideration of the sizeof the apparatus in which the distillative separation is carried out andthe amount of heat required by the distillative separation, the molarratio is more preferably within the range of from 1:0.2 to 1:300 andeven more preferably within the range of from 1:0.3 to 1:30, and can bedetermined while taking into consideration the ratio of the number ofmoles of the ester groups of carbamic acid ester in the finally obtainedcomposition of the present embodiment and the number of mole of aromatichydroxy compound, as well as the amount of aromatic hydroxy compounddistilled during distillative separation.

Although varying according to the composition of the liquid supplied tothe distillation apparatus where the distillative separation is carriedout, temperature, distillation apparatus and the like, the pressure atwhich the distillative separation is carried out may be a decreasedpressure, an atmospheric pressure or an increased pressure, andgenerally the distillative separation is preferably carried out withinthe range of from 0.01 kPa to 10 MPa, and in consideration of the easeof industrial application, is more preferably carried out at from 0.1kPa to 1 MPa and even more preferably carried out within the range offrom 0.5 kPa to 50 kPa.

Although known materials may be used for the apparatus and lines used tocarry out the distillative separation provided they do not have adetrimental effect on the starting substances or reactants, SUS304,SUS316 or SUS316L and the like can be used preferably since they areinexpensive. There are no particular limitations on the type ofdistillation apparatus, and a known distillation apparatus can be used.A distillation apparatus is preferably used that is provided with linesfor extracting alcohol, carbonic acid ester or urea from thedistillation apparatus in the form of a gaseous component during thedistillative separation, and for extracting a mixture containingcarbamic acid ester and aromatic hydroxy compound in liquid form fromthe bottom of the distillation apparatus. Various types of methods areused for the distillation apparatus, examples of which may include adistillation column, a multistage distillation column, a continuousmultistage distillation column, a packed column, a thin film evaporator,a falling film evaporator, a falling drop evaporator and combinationsthereof.

A multistage distillation column refers to a distillation column havingmultiple stages in which the number of theoretical plates ofdistillation is 2 or more, and any multistage distillation column may beused provided it allows continuous distillation. Any multistagedistillation column can be used for the multistage distillation columnprovided it is ordinarily used as a multistage distillation column,examples of which may include tray column types using a bubble tray, aporous plate tray, a valve tray or a counter-current tray, and a packedcolumn types packed with various types of packing materials such as araschig ring, a lessing ring, a pole ring, a Berl saddle, an Interlocksaddle, a Dixon packing, a McMahon packing, Helipack, a Sulzer packingor Mellapak. Any packed column can be used provided the column is packedwith a known packing material as described above. Moreover, acombination tray-packed column type is also used preferably thatcombines a tray portion with a portion packed with a packing material.The distillation column is preferably provided with a line for supplyinga reaction liquid obtained by producing carbamic acid ester and anaromatic hydroxy compound or a mixture thereof, a line for extractingthe alcohol and the carbonic acid ester or the urea in the form of agaseous phase component, and a line for extracting a mixed liquidcontaining the carbamic acid ester and the aromatic hydroxy compound,and the line for extracting the gaseous phase component is preferably ata location that allows the gaseous phase component of the apparatuswhere distillative separation is carried out to be extracted, and theline for extracting the mixed liquid containing the aryl carbamate andthe aromatic hydroxy compound is particularly preferably located therebelow. The alcohol and the carbonic acid ester or the urea may berespectively distilled and extracted in the apparatus where thedistillative separation is carried out, or may be extracted in the formof a mixture.

A line for supplying inert gas and/or liquid inert solvent from thelower portion of the reaction vessel may be separately attached, and inthe case the composition obtained by the distillation procedure containsundesired amounts of alcohol, carbonic acid ester or urea, a line may beattached for circulating all or a portion of the composition to theapparatus where distillation is carried out. Furthermore, in the case ofusing the above-mentioned inert solvent, the inert solvent may be in theform of a gas and/or a liquid.

Alcohol, carbonic acid ester, urea and azeotropic and/or accompanyingaromatic hydroxy compounds and the like extracted from the apparatus maybe recycled after purifying using the known method such as adistillation column. Equipment for warming, cooling or heating may beadded to each line in consideration of clogging and the like.

The ratio of the number of mole of ester groups of the carbamic acidester in the mixture of carbamic acid ester and aromatic hydroxycompound obtained by distillative separation and the number of mole ofthe aromatic hydroxy compound may be made to be a desired ratio byadding aromatic hydroxy compound to the mixture in the case the amountof aromatic hydroxy compound is low with respect to the desired molarratio. Conversely, the ratio of the number of mole of ester groups ofthe carbamic acid ester in the mixture of carbamic acid ester andaromatic hydroxy compound obtained by distillative separation and thenumber of mole of aromatic hydroxy compound may also be made to be adesired ratio by further separating the aromatic hydroxy compound bydistillation in the case the amount of the aromatic hydroxy compound ishigh with respect to the desired molar ratio.

In addition, the alcohol and/or carbonic acid ester or urea recovered instep (3) explained above can be reused in step (1) or step (2).

<Step (4)>

Step (4) is a step for transferring the composition obtained in step (3)to a reaction vessel where step (5) is carried out in a liquid state. Inthis step (4), the temperature during transfer of the composition ispreferably 180° C. or lower. When transferring the composition in aliquid form, although the composition is put into liquid form by heatingto a temperature equal to or higher than the temperature at which thecomposition becomes a homogeneous liquid, in the case the temperature atwhich the composition becomes a homogeneous liquid is higher than 180°C., thermal decomposition of the carbamic acid ester constituting thecomposition occurs when transforming the composition into the liquidform, thereby resulting in the case of isocyanate being formed atundesirable locations and making this undesirable. From such aviewpoint, the temperature at which the composition becomes ahomogeneous liquid is preferably 180° C. or lower, and in considerationof the ease of maintaining the temperature of the transfer line and thelike, the temperature is more preferably 150° C. or lower and even morepreferably 100° C. or lower.

<Step (5)>

Step (5) is a step for producing isocyanate using the compositiontransferred in step (4). Step (5) can be carried out by a method inwhich isocyanate is produced by subjecting the carbamic acid estercontained in the composition to a thermal decomposition reaction in thepresence of the aromatic hydroxy compound contained in the composition,a method in which isocyanate is produced by obtaining the aryl carbamatehaving a group derived from an aromatic hydroxy compound by reactingcarbamic acid ester contained in the composition with the aromatichydroxy compound contained in the composition, followed by subjectingthe aryl carbamate to a thermal decomposition reaction, or a method thatcombines these methods. The following provides an explanation of step(5). Step (5) can be carried out by the two methods indicated below.

<Direct Method>

As a first method for carrying out step (5), a method is explained inwhich isocyanate is produced by subjecting the carbamic acid estercontained in the composition to a thermal decomposition reaction in thepresence of the aromatic hydroxy compound contained in the composition.

The thermal decomposition reaction mainly contains a reaction that formsa corresponding isocyanate and hydroxy compound (alcohol or aromatichydroxy compound derived from a carbamic acid ester) from a carbamicacid ester, and is carried out in the presence of an aromatic hydroxycompound as described above.

Although reaction conditions vary according to the compounds used, thestoichiometric ratio of the amount of aromatic hydroxy compound used tothe carbamic acid ester used is preferably from 1 to 100 times. Althoughit is preferable to use a large amount of aromatic hydroxy compound toinhibit side reactions as previously described, in consideration of thesize of the reaction vessel and the like, the stoichiometric ratio ismore preferably from 2 to 80 times and even more preferably from 2 to 50times. An aromatic hydroxy compound of the same type as the aromatichydroxy compound contained in the composition may be further addedduring the thermal decomposition reaction, and the thermal decompositionreaction may also be carried out by adding the aromatic hydroxy compoundof a different type from the aromatic hydroxy compound contained in thecomposition in consideration of separation of the isocyanate formed, thehydroxy compound and the like.

The reaction temperature is generally within the range of from 100 to400° C., and although a high temperature is preferable for increasingthe reaction rate, since side reactions as described above may beconversely caused by the carbamic acid ester and/or the product in theform of the isocyanate, the reaction temperature is preferably withinthe range of from 130 to 300° C. and more preferably within the range offrom 150 to 250° C. A known cooling apparatus or heating apparatus maybe installed in the reaction vessel to maintain a constant reactiontemperature. In addition, although varying according to the types ofcompounds used and reaction temperature, the reaction pressure may be adecreased pressure, a normal pressure or an increased pressure, and thereaction is generally carried out at a pressure within the range of from20 to 1×10⁶ Pa. There are no particular limitations on the reaction time(residence time in the case of a continuous method) and is generallyfrom 0.001 to 100 hours, preferably from 0.01 to 50 hours and morepreferably from 0.1 to 30 hours. A catalyst can be used in the presentembodiment, and the catalyst is used at 0.01 to 30% by weight andpreferably at 0.5 to 20% by weight based on the weight of the arylcarbamate. For example, organic metal catalysts such as dibutyl tindilaurate, lead octoate or stannous octoate, or amines such as1,4-diazabicyclo[2,2,2]octane, triethylenediamine or triethylamine aresuitable for use as catalysts, while organic metal catalysts such asdibutyl tin dilaurate, lead octoate or stannous octoate are particularlypreferable. These compounds may be used alone or two or more types maybe used as a mixture.

A solvent can also be used in the present embodiment, and althoughexamples of solvents that can be used may include alkanes such aspentane (including isomers), hexane (including isomers), heptane(including isomers), octane (including isomers), nonane (includingisomers) or decane (including isomers); aromatic hydrocarbons andalkyl-substituted aromatic hydrocarbons such as benzene, toluene, xylene(including isomers), ethyl benzene, diisopropyl benzene (includingisomers), dibutyl benzene (including isomers) or naphthalene; nitrilecompounds such as acetonitrile or benzonitrile; aromatic compoundssubstituted with a halogen or nitro group such as chlorobenzene,dichlorobenzene (including isomers), bromobenzene, dibromobenzene(including isomers), chloronaphthalene, bromonaphthalene, nitrobenzeneor nitronaphthalene; polycyclic hydrocarbon compounds such as diphenyl,substituted diphenyl, diphenyl methane, terphenyl, anthracene ordibenzyl toluene (including isomers); aliphatic hydrocarbons such ascyclohexane, cyclopentane, cyclooctane or ethylcyclohexane; alicyclicalcohols such as cyclohexanol, cyclopentanol or cyclooctanol; ketonessuch as methyl ethyl ketone or acetophenone; esters such as dibutylphthalate, dihexyl phthalate, dioctyl phthalate or benzylbutylphthalate; ethers and thioethers such as tetrahydrofuran, 1,4-dioxane,1,2-dimethoxyethane, diphenyl ether or diphenyl sulfide; ketonecompounds such as acetone or methyl ethyl ketone; ester compounds suchas ethyl acetate or ethyl benzoate; and, sulfoxides such asdimethylsulfoxide or diphenylsulfoxide, based on the complexity of theprocedure during separation and recovery of the hydroxy compound, thecarbamic acid ester thermal decomposition reaction is preferably carriedout without using a solvent.

As was previously described, although the thermal decomposition reactionof the present embodiment is a reaction by which a correspondingisocyanate and a hydroxy compound are formed from the carbamic acidester, the thermal decomposition reaction is an equilibrium reaction.Thus, in order to efficiently obtain isocyanate in this thermaldecomposition reaction, it is preferable to remove at least one of theproducts of this thermal decomposition reaction in the form of theisocyanate and the hydroxy compound from the thermal decompositionreaction system in the form of a gaseous component by a method such asdistillation. Whether the isocyanate or hydroxy compound is removed as agaseous component can be arbitrarily determined according to thecompounds used, and for example, the respective normal boiling points ofthe isocyanate and the hydroxy compound are compared followed byremoving the compound having the lower normal boiling point in the formof a gaseous component.

The thermal decomposition reaction is preferably carried out by acontinuous method. A continuous method refers to a method in which thecarbamic acid ester is continuously supplied to a reaction vessel whereit is subjected to a thermal decomposition reaction, and at least eitherthe formed isocyanate or hydroxy compound is removed from the reactionvessel in the form of a gaseous component, while a portion or all of theliquid containing the carbamic acid ester and/or aromatic hydroxycompound is removed from the bottom of the reaction vessel.

In the case of carrying out the carbamic acid ester thermaldecomposition reaction using a continuous method, the carbamic acidester is supplied to the reaction vessel where the thermal decompositionreaction is carried out in the form of a composition with an aromatichydroxy compound of the present embodiment. Although there are manycases in which the carbamic acid ester is a solid at normal temperatures(e.g., 25° C.), since there many cases in which the composition of thepresent embodiment is a liquid, there are many cases in which it isadvantageous in terms of continuously supplying to the reaction vessel.In addition, since there are many case in which it is advantageous forthe composition of the present embodiment to have a low viscosity whentransferring the composition to the reaction vessel, there are manycases in which the composition is supplied to the reaction vessel whilemaintaining at a certain temperature (for example, 130° C.). Althoughside reactions occur as described above ultimately leading to a decreasein the yield of isocyanate if the carbamic acid ester is held at thesetemperature conditions for a long period of time, the inventors of thepresent invention surprisingly found that the composition of the presentembodiment is resistant to the occurrence of such side reactions even ifheld under such temperature conditions for a long period of time.Although the mechanism by which these aromatic hydroxy compounds inhibitside reactions is not clear, as previously described, the inventors ofthe present invention presumed that, as a result of an aromatic hydroxycompound forming hydrogen bonds between urethane bonds (—NHCOO—) of thecarbamic acid ester and the aromatic hydroxy compound, a state is formedin which the urethane bonds have difficulty in approaching each other,thereby making it difficult for a reaction that forms urea bonds tooccur as in, for example, a reaction that forms urea bonds representedby the above-mentioned formula (2).

Although known materials may be used for the reaction vessel and linesused to carry out the thermal decomposition reaction provided they donot have a detrimental effect on the carbamic acid ester or the productsin the form of the hydroxy compound and isocyanate, SUS304, SUS316 orSUS316L and the like can be used preferably since they are inexpensive.There are no particular limitations on the type of reaction vessel, anda known tank type reaction vessel or a column type reaction vessel canbe used. A reaction vessel is preferably used that is provided withlines for extracting a low boiling point mixture containing at leasteither the isocyanate or the hydroxy compound formed in the thermaldecomposition reaction from the reaction vessel in the form of a gaseouscomponent, and for removing all or a portion of a mixed liquidcontaining unreacted carbamic acid ester and compounds not extracted inthe form of a gaseous component from the lower portion of the reactionvessel. Various known methods are used for such a reaction vessel,examples of which may include types using reaction vessels containing astirring tank, a multistage stirring tank, a distillation column, amultistage distillation column, a multitubular reactor, a continuousmultistage distillation column, a packed column, a thin film evaporator,a reactor provided with a support inside, a forced circulation reactor,a falling film evaporator, a falling drop evaporator, a trickle flowreactor or a bubble column, and types using combinations thereof.Methods using a thin film evaporator or a columnar reaction vessel arepreferable from the viewpoint of rapidly removing the low boiling pointcomponent from the reaction system, while a structure having a largegas-liquid contact area is preferable for rapidly transferring the lowboiling point component formed to the gaseous phase.

The reaction vessel is preferably provided with a line for supplying thecarbamic acid ester, a line for extracting a gaseous componentcontaining at least either the isocyanate or the hydroxy compound formedby the thermal decomposition reaction, and a line for extracting a mixedliquid containing compounds not removed as a gaseous component andunreacted carbamic acid ester, and the line for extracting the gaseouscomponent containing at least either the isocyanate or hydroxy compoundis preferably located at a location that allows the gaseous component inthe reaction vessel to be extracted, and the line for extracting themixed liquid containing compounds not removed as a gaseous component,unreacted carbamic acid ester and the aromatic hydroxy compound isparticularly preferably located there below.

In addition, a line for supplying inert gas and/or liquid inert solventfrom the lower portion of the reaction vessel may be separatelyattached, and a line may also be attached for recirculating all or aportion of the mixed liquid containing unreacted carbamic acid esterand/or active hydrogen extracted from the bottom of the reaction vessel.Equipment for warming, cooling or heating may be added to each line inconsideration of clogging and the like.

Although there are many cases in which the gaseous component removedfrom the thermal decomposition reaction, and/or the mixed liquidcontaining compounds not removed as a gaseous component, unreactedcarbamic acid ester and aromatic hydroxy compound containing aromatichydroxy compounds and/or alcohols in the form of compounds other thanisocyanates, among these compounds, the aromatic hydroxy compound can bereused as the aromatic hydroxy compound of step (3). On the other hand,the alcohol can be reused as the alcohol used in production of thedialkyl tin compound of step (A) in the process for producing carbonicacid ester, and the alcohol can also be reused during production ofcarbamic acid ester from an amine compound, alcohol and urea.

<Transesterification reaction and Decomposition Method>

A method is explained for the second method of step (5) for producingisocyanate by reacting the carbamic acid ester contained in thecomposition of step (4) with the aromatic hydroxy compound contained inthe composition to obtain the aryl carbamate having a group derived fromthe aromatic hydroxy compound followed by subjecting the aryl carbamateto a thermal decomposition reaction.

This process comprises the following steps (5-1) and (5-2):

step (5-1): reacting the carbamic acid ester and aromatic hydroxycompound which are contained in the composition of step (4), a lowboiling point component formed being recovered in a form of a gaseouscomponent, and a reaction liquid containing the aryl carbamate and thearomatic hydroxy compound being removed from a bottom of the reactionvessel in which the reaction occurs, and

step (5-2): supplying the reaction liquid of step (5-1) to a reactionvessel in which a thermal decomposition reaction occurs, the arylcarbamate being subjected to a thermal decomposition reaction, at leastone of either an isocyanate or an aromatic hydroxy compound which areformed being recovered in a form of a gaseous component, and all or aportion of a mixture containing the isocyanate and/or the aromatichydroxy compound and/or the aryl carbamate not recovered in a form of agaseous component being recovered from the bottom of the reactionvessel.

<Step (5-1)>

In step (5-1), the carbamic acid ester and the aromatic hydroxy compoundare reacted to obtain the aryl carbamate having a group derived from thearomatic hydroxy compound. In this reaction, an ester group of thecarbamic acid ester is replaced with an aryloxy group derived from thearomatic hydroxy compound resulting in the formation of thecorresponding aryl carbamate and a hydroxy compound derived from thecarbamic acid ester (also referred to as a “transesterificationreaction” in the present description).

Although varying according to the reacted compounds, the reactionconditions of this transesterification reaction are such that thearomatic hydroxy compound is used within the range of from 2 to 1000times the ester group of the carbamic acid ester when expressed as thestoichiometric ratio. As a result of conducting extensive studies, theinventors of the present invention surprisingly found that by using anaromatic hydroxy compound having a substituent at least one orthoposition with respect to the hydroxyl group in this transesterificationreaction as previously described, side reactions as previously describedattributable to the carbamic acid ester and/or product in the form ofthe aryl carbamate can be inhibited in the transesterification reaction.In the transesterification reaction, although the aromatic hydroxycompound is preferably used in excess with respect to the ester group ofthe carbamic acid ester in order to inhibit side reactions attributableto the carbamic acid ester and/or product in the form of the arylcarbamate as well as allow the reaction to be completed quickly, thearomatic hydroxy compound is preferably used within the range of from 2to 100 times and preferably within the range of from 5 to 50 times inconsideration of the size of the reaction vessel.

During the transesterification reaction, an aromatic hydroxy compound ofthe same type as the aromatic hydroxy compound contained in thecomposition may be further added, or the thermal decomposition reactionmay be carried out by adding a different type of aromatic hydroxycompound from the aromatic hydroxy compound contained in the compositionin consideration of separation of the resulting isocyanate, hydroxycompound and the like.

The reaction temperature is generally within the range of from 100 to300° C., and although high temperatures are preferable in order toincrease the reaction rate, since there conversely may be greatersusceptibility to the occurrence of side reactions at high temperatures,the reaction temperature is preferably within the range of from 150 to250° C. A known cooling apparatus or heating apparatus may be installedin the reaction vessel to maintain a constant reaction temperature. Inaddition, although varying according to the types of compounds used andreaction temperature, the reaction pressure may be a decreased pressure,a normal pressure or an increased pressure, and the reaction isgenerally carried out at a pressure within the range of from 20 to 1×10⁶Pa. There are no particular limitations on the reaction time (residencetime in the case of a continuous method) and is generally from 0.001 to100 hours, preferably from 0.01 to 50 hours and more preferably from 0.1to 30 hours. In addition, the reaction can also be completed byconfirming that a desired amount of aryl carbamate has been formed by,for example, liquid chromatography after sampling the reaction liquid.In the present embodiment, the catalyst is used at 0.01 to 30% by weightand preferably at 0.5 to 20% by weight based on the weight of thecarbamic acid ester. For example, organic metal catalysts such asdibutyl tin dilaurate, lead octoate or stannous octoate, or amines suchas 1,4-diazabicyclo[2,2,2]octane, triethylenediamine or triethylamineare suitable for use, while organic metal catalysts such as dibutyl tindilaurate, lead octoate or stannous octoate are particularly preferable.These compounds may be used alone or two or more types may be used as amixture.

Although the use of a reaction solvent is not necessarily required inthe present embodiment, a suitable inert solvent is preferably used as areaction solvent for the purpose of facilitating the reaction procedure,examples of which may include alkanes such as hexane (includingisomers), heptane (including isomers), octane (including isomers),nonane (including isomers) or decane (including isomers); aromatichydrocarbons and alkyl-substituted aromatic hydrocarbons such asbenzene, toluene, xylene (including isomers), ethyl benzene, diisopropylbenzene (including isomers), dibutyl benzene (including isomers) ornaphthalene; aromatic compounds substituted with a halogen or nitrogroup such as chlorobenzene, dichlorobenzene (including isomers),bromobenzene, dibromobenzene (including isomers), chloronaphthalene,bromonaphthalene, nitrobenzene or nitronaphthalene; polycyclichydrocarbon compounds such as diphenyl, substituted diphenyl, diphenylmethane, terphenyl, anthracene or dibenzyl toluene (including isomers);aliphatic hydrocarbons such as cyclohexane, cyclopentane, cyclooctane orethylcyclohexane; ketones such as methyl ethyl ketone or acetophenone;esters such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalateor benzylbutyl phthalate; ethers and thioethers such as diphenyl etheror diphenyl sulfide; and sulfoxides such as dimethylsulfoxide ordiphenylsulfoxide; and, silicone oil. These solvents can be used aloneor two or more types can be used as a mixture.

As has been previously described, although the transesterificationreaction in the present embodiment involves an exchange between an estergroup of the carbamic acid ester and an aryloxy group derived from thearomatic hydroxy compound resulting in the formation of thecorresponding aryl carbamate and an alcohol, the transesterificationreaction is an equilibrium reaction. Thus, in order to efficientlyproduce the aryl carbamate by this transesterification reaction, it ispreferable to remove the products from the reaction system. Since thecompound having the lowest normal boiling point in the reaction systemis the alcohol formed by the transesterification reaction, the alcoholis preferably removed from the reaction system by a method such asdistillative separation.

In addition, the transesterification reaction is preferably carried outby a continuous method to allow the transesterification reaction toproceed efficiently. Namely, a method is preferably used in which thecarbamic acid ester and the aromatic hydroxy compound are suppliedcontinuously to the reaction vessel to carry out the transesterificationreaction, the alcohol formed is removed from the reaction vessel in theform of a gaseous component, and a reaction liquid containing the formedaryl carbamate and the aromatic hydroxy compound is continuously removedfrom the bottom of the reaction vessel. In the case of carrying out thetransesterification reaction according to this method, in addition topromoting the transesterification reaction, there is also the unexpectedeffect of being able to improve the final yield of isocyanate byinhibiting side reactions as previously described.

Although known materials may be used for the reaction vessel and linesused to carry out the transesterification reaction provided they do nothave a detrimental effect on the starting substances or reactants,SUS304, SUS316 or SUS316L and the like can be used preferably since theyare inexpensive. There are no particular limitations on the type ofreaction vessel, and a known tank-type or a column-type reaction vesselcan be used. A reaction vessel is preferably used that is provided withlines for extracting a low boiling point reaction mixture containingalcohol formed in the transesterification reaction from the reactionvessel in the form of a gaseous component, and for extracting a mixedliquid containing the produced aryl carbamate and aromatic hydroxycompound from the lower portion of the reaction vessel in the form of aliquid. Various known methods are used for such a reaction vessel,examples of which may include types using reaction vessels containing astirring tank, a multistage stirring tank, a distillation column, amultistage distillation column, a multitubular reactor, a continuousmultistage distillation column, a packed column, a thin film evaporator,a reactor provided with a support inside, a forced circulation reactor,a falling film evaporator, a falling drop evaporator, a trickle flowreactor or a bubble column, and types using combinations thereof.Methods using a thin film evaporator or a columnar reactor arepreferable from the viewpoint of efficiently shifting the equilibrium tothe products side, while a structure having a large gas-liquid contactarea is preferable for being able to rapidly transfer the alcohol formedto the gaseous phase.

A multistage distillation column refers to a distillation column havingmultiple stages in which the number of theoretical plates ofdistillation is 2 or more, and any multistage distillation column may beused provided it allows continuous distillation. Any multistagedistillation column can be used for the multistage distillation columnprovided it is ordinarily used as a multistage distillation column,examples of which may include tray column types using a bubble tray, aporous plate tray, a valve tray or a counter-current tray, and packedcolumn types packed with various types of packing materials such as araschig ring, a lessing ring, a pole ring, a Berl saddle, an Interlocksaddle, a Dixon packing, a McMahon packing, Helipack, a Sulzer packingor Mellapak. Any packed column can be used provided the column is packedwith a known packing material as described above. Moreover, acombination tray-packed column type is also used preferably thatcombines a tray portion with a portion packed with a packing material.The reaction vessel is preferably provided with a line for supplying amixture containing the carbamic acid ester and the aromatic hydroxycompound, a line for extracting a gaseous phase component containingalcohol formed by the transesterification reaction, and a line forextracting a mixed liquid containing the aryl carbamate and aromatichydroxy compound, and the line for extracting the gaseous phasecomponent containing the alcohol is preferably at a location that allowsthe gaseous phase component in the reaction vessel to be extracted, andthe line for extracting the mixed liquid containing the aryl carbamateand the aromatic hydroxy compound is particularly preferably locatedthere below.

A line for supplying inert gas and/or liquid inert solvent from thelower portion of the reaction vessel may be separately attached, and inthe case the mixed liquid containing the formed aryl carbamate and thearomatic hydroxy compound contains unreacted carbamic acid ester, a linemay be attached for recirculating all or a portion of the mixed liquidto the reaction vessel. Furthermore, in the case of using theabove-mentioned inert solvent, the inert solvent may be in the form of agas and/or a liquid.

The gaseous component containing alcohol extracted from the reactionvessel may be purified using a known method such as a distillationcolumn, and the azeotropic and/or accompanying aromatic hydroxy compoundand the like may be recycled. Equipment for warming, cooling or heatingmay be added to each line in consideration of clogging and the like.

The aryl carbamate preferably produced by the transesterificationreaction is an aryl carbamate represented by any of the followingformulas (32) to (34):

(wherein ring B represents a structure containing at least one structureselected from the group consisting of a benzene ring, naphthalene ringand anthracene ring, the structure may have a substituent,

R²¹ represents a group other than a hydrogen atom in a form of analiphatic alkyl group having 1 to 20 carbon atoms, an aliphatic alkoxygroup having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbonatoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyl grouphaving 7 to 20 carbon atoms or an aralkyloxy group having 7 to 20 carbonatoms, the above groups containing an atom selected from the groupconsisting of carbon, oxygen and nitrogen atoms, and

R²² represents an aliphatic alkyl group having 1 to 20 carbon atoms, analiphatic alkoxy group having 1 to 20 carbon atoms, an aryl group having6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, anaralkyl group having 7 to 20 carbon atoms or an aralkyloxy group having7 to 20 carbon atoms, the above groups containing an atom selected fromthe group consisting of carbon, oxygen and nitrogen atoms).

Among these, a more preferably produced aryl carbamate is an arylcarbamate represented by any of the following formulas (35) to (37):

(wherein R²¹ represents a group other than a hydrogen atom in a form ofan aliphatic alkyl group having 1 to 20 carbon atoms, an aliphaticalkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkylgroup having 7 to 20 carbon atoms or an aralkyloxy group having 7 to 20carbon atoms, the above groups containing an atom selected from thegroup consisting of carbon, oxygen and nitrogen atoms, and

each of R²², R²³, R²⁴ and R²⁵ independently represents an aliphaticalkyl group having 1 to 20 carbon atoms, an aliphatic alkoxy grouphaving 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,an aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7to 20 carbon atoms or an aralkyloxy group having 7 to 20 carbon atoms,the above groups containing an atom selected from the group consistingof carbon, oxygen and nitrogen atoms, or a hydrogen atom).

Examples of aryl carbamates represented by formula (35) may includeN,N′-hexanediyl-bis-carbamic acid bis(2-ethylphenyl)ester,N,N′-hexanediyl-bis-carbamic acid bis(2-propylphenyl)ester (includingisomers), N,N′-hexanediyl-bis-carbamic acid bis(2-butylphenyl)ester(including isomers), N,N′-hexanediyl-bis-carbamic acidbis(2-pentylphenyl)ester (including isomers),N,N′-hexanediyl-bis-carbamic acid bis(2-hexylphenyl)ester (includingisomers), N,N′-hexanediyl-bis-carbamic acid bis(2-octylphenyl)ester(including isomers), N,N′-hexanediyl-bis-carbamic acidbis(2-cumylphenyl)ester, N,N′-hexanediyl-bis-carbamic acidbis(2,4-diethylphenyl)ester, N,N′-hexanediyl-bis-carbamic acidbis(2,4-dipropylphenyl)ester (including isomers),N,N′-hexanediyl-bis-carbamic acid bis(2,4-dibutylphenyl)ester (includingisomers), N,N′-hexanediyl-bis-carbamic acid bis(2,4-dipentylphenyl)ester(including isomers), N,N′-hexanediyl-bis-carbamic acidbis(2,4-dihexylphenyl)ester (including isomers),N,N′-hexanediyl-bis-carbamic acid bis(2,4-dioctylphenyl)ester (includingisomers), N,N′-hexanediyl-bis-carbamic acid bis(2,4-dicumylphenyl)ester(including isomers), N,N′-hexanediyl-bis-carbamic acidbis(2,6-dimethylphenyl)ester, N,N′-hexanediyl-bis-carbamic acidbis(2,6-diethylphenyl)ester (including isomers),N,N′-hexanediyl-bis-carbamic acid bis(2,6-dipropylphenyl)ester(including isomers), N,N′-hexanediyl-bis-carbamic acidbis(2,4,6-trimethylphenyl)ester, N,N′-hexanediyl-bis-carbamic acidbis(2,3,6-trimethylphenyl)ester, N,N′-hexanediyl-bis-carbamic acidbis(2,4,6-triethylphenyl)ester, and N,N′-hexanediyl-bis-carbamic acidbis(2,4,6-tripropylphenyl)ester (including isomers). In addition,examples of alkyl carbamates represented by formula (36) includebis(2-ethylphenyl)-4,4′-methylene-dicyclohexyl carbamate,bis(2-propylphenyl)-4,4′-methylene-dicyclohexyl carbamate (includingisomers), bis(2-butylphenyl)-4,4′-methylene-dicyclohexyl carbamate(including isomers), bis(2-pentylphenyl)-4,4′-methylene-dicyclohexylcarbamate (including isomers),bis(2-hexylphenyl)-4,4′-methylene-dicyclohexyl carbamate (includingisomers), bis(2-heptylphenyl)-4,4′-methylene-dicyclohexyl carbamate(including isomers), bis(2-octylphenyl)-4,4′-methylene-dicyclohexylcarbamate (including isomers),bis(2-cumylphenyl)-4,4′-methylene-dicyclohexyl carbamate,bis(2,4-diethylphenyl)-4,4′-methylene-dicyclohexyl carbamate (includingisomers), bis(2,4-dipropylphenyl)-4,4′-methylene-dicyclohexyl carbamate(including isomers), bis(2,4-dibutylphenyl)-4,4′-methylene-dicyclohexylcarbamate (including isomers),bis(2,4-dipentylphenyl)-4,4′-methylene-dicyclohexyl carbamate (includingisomers), bis(2,4-dihexylphenyl)-4,4′-methylene-dicyclohexyl carbamate(including isomers), bis(2,4-diheptylphenyl)-4,4′-methylene-dicyclohexylcarbamate (including isomers),bis(2,4-dioctylphenyl)-4,4′-methylene-dicyclohexyl carbamate (includingisomers), bis(2,4-dicumylphenyl)-4,4′-methylene-dicyclohexyl carbamate,bis(2,6-dimethylphenyl)-4,4′-methylene-dicyclohexyl carbamate (includingisomers), bis(2,6-diethylphenyl)-4,4′-methylene-dicyclohexyl carbamate(including isomers), bis(2,6-dipropylphenyl)-4,4′-methylene-dicyclohexylcarbamate (including isomers),bis(2,4,6-trimethylphenyl)-4,4′-methylene-dicyclohexyl carbamate(including isomers),bis(2,4,6-triethylphenyl)-4,4′-methylene-dicyclohexyl carbamate(including isomers) andbis(2,4,6-tripropylphenyl)-4,4′-methylene-dicyclohexyl carbamate(including isomers). Moreover, examples of alkyl carbamates representedby formula (37) may include3-((2-ethylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2-ethylphenyl)ester,3-((2-propylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid 2-propylphenyl)ester (including isomers),3-((2-butylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2-butylphenoxy)ester (including isomers),3-((2-pentylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2-pentylphenyl)ester (including isomers),3-((2-hexylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2-hexylphenyl)ester (including isomers),3-((2-heptylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2-heptylphenyl)ester (including isomers),3-((2-octylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2-octylphenyl)ester (including isomers),3-((2-cumylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2-cumylphenyl)ester (including isomers),3-((2,4-diethylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,4-diethylphenyl)ester,3-((2,4-dipropylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,4-dipropylphenyl)ester (including isomers),3-((2,4-dibutylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,4-dibutylphenyl)ester (including isomers),3-((2,4-dipentylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,4-dipentylphenyl)ester (including isomers),3-((2,4-dihexylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,4-dihexylphenyl)ester (including isomers),3-((2,4-diheptylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,4-diheptylphenyl)ester (including isomers),3-((2,4-dioctylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,4-dioctylphenyl)ester (including isomers),3-((2,4-dicumylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,4-dicumylphenyl)ester,3-((2,6-dimethylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,6-dimethylphenyl)ester,3-((2,6-diethylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,6-diethyl phenyl)ester,3-((2,6-dipropylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,6-dipropylphenyl)ester (including isomers),3-((2,4,6-trimethyl phenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexyl carbamic acid (2,4,6-trimethylphenyl)ester,3-((2,4,6-triethylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,4,6-triethylphenyl)ester, and3-((2,4,6-tripropylphenoxy)carbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acid (2,4,6-tripropylphenyl)ester (including isomers).

The aryl carbamate produced in the transesterification reaction may besubjected to the subsequent thermal decomposition reaction while stillas a mixed liquid containing aryl carbamate and aromatic hydroxycompound removed from the reaction vessel, or the aryl carbamate may besubjected to the thermal decomposition reaction after purifying from themixed liquid. A known method can be used to purify the aryl carbamatefrom the reaction liquid, examples of which may include removal of thearomatic hydroxy compound by distillation, washing with a solvent andpurification of the aryl carbamate by crystallization.

Since the aryl carbamate of the present embodiment is a carbamic acidester composed of an aromatic hydroxy compound and an isocyanate, thethermal decomposition temperature is low as is generally known. Inaddition, the aryl carbamate of the present embodiment is unexpectedlyextremely resistant to the occurrence of side reactions (such as areaction resulting in the formation of a urea bond as previouslydescribed) at high temperatures (such as 200° C.) at which the thermaldecomposition reaction is carried out. Although the mechanism by whichside reactions are inhibited is unclear, as was previously described, itis presumed that a substituent at the ortho position relative to thehydroxyl group sterically protects a urethane bond, thereby hinderingthe reaction between a different carbamic acid ester and the urethanebond.

Moreover, although the aromatic hydroxy compound formed by the thermaldecomposition reaction of the aryl carbamate of the present embodimentis an aromatic hydroxy compound having a substituent at the orthoposition relative to a hydroxyl group, since the reaction rate betweenthe aromatic hydroxy compound and isocyanate is surprisingly slow,namely the reverse reaction rate in the thermal decomposition reactionis surprisingly low, when carrying out the thermal decompositionreaction on the aryl carbamate, there is the advantage of being able toeasily separate the aromatic hydroxy compound and the isocyanate.

The alcohol derived from carbamic acid ester formed in theabove-mentioned transesterificaion reaction step can be reused as thealcohol used to produce the dialkyl tin compound of step (A) in theprocess for producing carbonic acid ester, or it can be reused as thealcohol used when producing carbamic acid ester from an amine compound,alcohol and urea.

<Step (5-2)>

The following provides an explanation of the aryl carbamatedecomposition reaction of step (5-2).

The decomposition reaction of the present embodiment is a thermaldecomposition reaction by which the corresponding isocyanate and thearomatic hydroxy compound are formed from the aryl carbamate.

The reaction temperature is generally within the range of from 100 to300° C., and although a high temperature is preferable for increasingthe reaction rate, since side reactions as described above may beconversely caused by the aryl carbamate and/or the reaction product inthe form of the isocyanate, the reaction temperature is preferablywithin the range of from 150 to 250° C. A known cooling apparatus orheating apparatus may be installed in the reaction vessel to maintain aconstant reaction temperature. In addition, although varying accordingto the types of compounds used and reaction temperature, the reactionpressure may be a decreased pressure, a normal pressure or an increasedpressure, and the reaction is generally carried out at a pressure withinthe range of from 20 to 1×10⁶ Pa. There are no particular limitations onthe reaction time (residence time in the case of a continuous method)and is generally from 0.001 to 100 hours, preferably from 0.01 to 50hours and more preferably from 0.1 to 30 hours. A catalyst can be usedin the present embodiment, and the catalyst is used at 0.01 to 30% byweight and preferably at 0.5 to 20% by weight based on the weight of thearyl carbamate. For example, organic metal catalysts such as dibutyl tindilaurate, lead octoate or stannous octoate, or amines such as1,4-diazabicyclo[2,2,2]octane, triethylenediamine or triethylamine aresuitable for use as catalysts, while organic metal catalysts such asdibutyl tin dilaurate, lead octoate or stannous octoate are particularlypreferable. These compounds may be used alone or two or more types maybe used as a mixture. In the case of using a catalyst in theabove-mentioned transesterification reaction, the catalyst contained inthe mixed liquid following the transesterification reaction may be usedas a catalyst in the thermal decomposition reaction or catalyst may befreshly added to the aryl carbamate when the thermal decompositionreaction is carried out.

Although the use of a reaction solvent is not necessarily required inthe present embodiment, a suitable inert solvent can be used as areaction solvent for the purpose of facilitating the reaction procedure,examples of which may include alkanes such as hexane (includingisomers), heptane (including isomers), octane (including isomers),nonane (including isomers) or decane (including isomers); aromatichydrocarbons and alkyl-substituted aromatic hydrocarbons such asbenzene, toluene, xylene (including isomers), ethyl benzene, diisopropylbenzene (including isomers), dibutyl benzene (including isomers) ornaphthalene; aromatic compounds substituted with a halogen or nitrogroup such as chlorobenzene, dichlorobenzene (including isomers),bromobenzene, dibromobenzene (including isomers), chloronaphthalene,bromonaphthalene, nitrobenzene or nitronaphthalene; polycyclichydrocarbon compounds such as diphenyl, substituted diphenyl, diphenylmethane, terphenyl, anthracene or dibenzyl toluene (including isomers);aliphatic hydrocarbons such as cyclohexane, cyclopentane, cyclooctane orethylcyclohexane; ketones such as methyl ethyl ketone or acetophenone;esters such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalateor benzylbutyl phthalate; ethers and thioethers such as diphenyl etheror diphenyl sulfide; and sulfoxides such as dimethylsulfoxide ordiphenylsulfoxide; and, silicone oil. These solvents can be used aloneor two or more types can be used as a mixture.

As was previously described, although the thermal decomposition reactionof the present embodiment is a reaction by which the correspondingisocyanate and the aromatic hydroxy compound are formed from the arylcarbamate, the thermal decomposition reaction is an equilibriumreaction. Thus, in order to efficiently obtain isocyanate in thisthermal decomposition reaction, it is preferable to remove at least oneof the products of this thermal decomposition reaction in the form ofthe isocyanate and the aromatic hydroxy compound from the thermaldecomposition reaction system in the form of a gaseous component by amethod such as distillation. Whether the isocyanate or the aromatichydroxy compound is removed as a gaseous component can be arbitrarilydetermined according to the compounds used, and for example, therespective normal boiling points of the isocyanate and the aromatichydroxy compound are compared followed by removing the compound havingthe lower normal boiling point in the form of a gaseous component.

The aryl carbamate is also susceptible to the occurrence of sidereactions as described above in the case of being held at a hightemperature for a long period of time, although to a much lower degreethan carbamic acid ester. In addition, the above-mentioned sidereactions may also be induced by the isocyanate formed by the thermaldecomposition reaction. Thus, the time during which the aryl carbamateand the isocyanate are held at a high temperature is preferably as shortas possible, and the thermal decomposition reaction is preferablycarried out by a continuous method. A continuous method refers to amethod in which the aryl carbamate is continuously supplied to thereaction vessel where it is subjected to a thermal decompositionreaction, and at least either the formed isocyanate or aromatic hydroxycompound is removed from the reaction vessel in the form of a gaseouscomponent.

Although known materials may be used for the reaction vessel and linesused to carry out the thermal decomposition reaction provided they donot have a detrimental effect on the aryl carbamate or the products inthe form of the aromatic hydroxy compound and isocyanate, SUS304, SUS316or SUS316L and the like can be used preferably since they areinexpensive. There are no particular limitations on the type of reactionvessel, and a known tank-type reaction vessel or a column-type reactionvessel can be used. A reaction vessel is preferably used that isprovided with lines for extracting a low boiling point mixturecontaining at least either the isocyanate or the aromatic hydroxycompound formed in the thermal decomposition reaction from the reactionvessel in the form of a gaseous component, and for removing a mixedliquid containing unreacted aryl carbamate and compounds not extractedin the form of a liquid from the lower portion of the reaction vessel.Various known methods are used for such a reaction vessel, examples ofwhich may include types using reaction vessels containing a stirringtank, a multistage stirring tank, a distillation column, a multistagedistillation column, a multitubular reactor, a continuous multistagedistillation column, a packed column, a thin film evaporator, a reactorprovided with a support inside, a forced circulation reactor, a fallingfilm evaporator, a falling drop evaporator, a trickle flow reactor or abubble column, and types using combinations thereof. Methods using athin film evaporator or a columnar reactor are preferable from theviewpoint of rapidly removing a low boiling point component from thereaction system, while a structure having a large gas-liquid contactarea is preferable for rapidly transferring the low boiling pointcomponent formed to the gaseous phase.

The reaction vessel is preferably provided with a line for supplying thearyl carbamate, a line for extracting a gaseous component containing atleast either the isocyanate or the aromatic hydroxy compound formed bythe thermal decomposition reaction, and a line for extracting a mixedliquid containing compounds not removed as a gaseous component andunreacted aryl carbamate, the line for extracting the gaseous componentcontaining at least either the isocyanate or the aromatic hydroxycompound is preferably located at a location that allows the gaseouscomponent in the reaction vessel to be extracted, and the line forextracting the mixed liquid containing compounds not removed as agaseous component and unreacted aryl carbamate is particularlypreferably located there below.

In addition, a line for supplying inert gas and/or liquid inert solventfrom the lower portion of the reaction vessel may be separatelyattached, and a line may also be attached for recirculating all or aportion of the mixed liquid containing unreacted aryl carbamate andcompounds not removed as a gaseous component to the reaction vessel.Equipment for warming, cooling or heating may be added to each line inconsideration of clogging and the like. Furthermore, in the case ofusing the above-mentioned inert solvent, the inert solvent may be in theform of a gas and/or a liquid.

The aromatic hydroxy compound obtained in the thermal decompositionreaction can be reused as the aromatic hydroxy compound in step (3) inthe process for producing the composition of the present embodiment.When reusing the aromatic hydroxy compound, the aromatic hydroxycompound may be reused after purifying by a known method such asdistillative purification. In addition, the entire amount of thearomatic hydroxy compound obtained in the thermal decomposition reactionmay be reused or only a portion thereof may be reused.

Table 1 is a table showing the process flow of an example of a modifiedprocess for producing isocyanate combining the composition of thepresent embodiment, a step for producing carbonic acid ester and thecomposition using the carbonic acid ester, a step for producingisocyanate using the composition, and the reuse of alcohol and/oraromatic hydroxy compound obtained in each step.

Table 1

TABLE 1

A mixture is produced containing the carbonic acid ester produced bygoing through steps (A) and (B) and the carbamic ester in step (1) usingamine compounds. The excess carbonic acid ester and by-product alcoholcontained in this mixture are subjected to distillative separation instep (3) in the presence of aromatic hydroxy compound to obtain thecomposition of the present embodiment containing carbamic acid ester andthe aromatic hydroxy compound. The alcohol is reused as the alcohol inthe regeneration step of the dialkyl tin compound of step (C), while thecarbonic acid ester is reused as the carbonic acid ester of step (1).Next, although isocyanate is produced using the composition of thepresent embodiment obtained in step (3), the production of isocyanatemay be carried out by a method in which isocyanate is produced bysubjecting the composition to a transesterification reaction aspreviously described, by a method in which isocyanate is produced byproducing the aryl carbamate by subjecting the composition to atransesterification reaction and then subjecting the aryl carbamate to athermal decomposition reaction, or by a method that combines both. Inthe isocyanate production step, the alcohol derived from the separatedcarbamic acid ester and the aromatic hydroxy compound are reused in thedialkyl tin compound regeneration step of step (C) and the step forproducing the composition containing the carbamic acid ester and thearomatic hydroxy compound of step (3), respectively. They may also besubjected to a purification step and the like in addition to the stepsdescribed above.

The composition of the present embodiment as described above is acomposition suitable for transfer and storage of carbamic acid ester,and this composition enables reductions in yield of carbamic acid estercaused by thermal denaturation and the like to be inhibited. Inaddition, the composition can also be used in the production ofisocyanate, and isocyanate produced with this composition can bepreferably used as a production raw material of polyurethane foam,paints, adhesives and the like, thereby making it extremely importantindustrially.

EXAMPLES

Although the following provides a detailed explanation of the presentinvention based on examples thereof, the scope of the present inventionis not limited by these examples.

<Analytical Methods>

1) NMR Analysis

-   -   Apparatus: JNM-A400 FT-N MR system, JEOL Ltd., Japan

(1) Preparation of ¹H—, ¹³C— and ¹¹⁹Sn-NMR Analysis Samples

About 0.3 g of sample solution were weighed followed by the addition ofabout 0.7 g of heavy chloroform (99.8%, Aldrich Corp., USA) and about0.05 g of internal standard in the form of tetramethyl tin (guaranteedreagent, Wako Pure Chemical Industries, Ltd., Japan) and mixing touniformity to obtain solutions used as NMR analysis samples.

(2) Quantitative Analysis

Analyses were performed for each standard and quantitative analyses wereperformed on the analysis sample solutions based on the resultingcalibration curve.

2) Liquid Chromatography

-   -   Apparatus: LC-10AT system, Shimadzu Corp., Japan    -   Column: Silica-60 column, Tosoh Corp., Japan, two columns        connected in series    -   Developing solvent: Mixed liquid of hexane/tetrahydrofuran        (80/20) (v/v)    -   Solvent flow rate: 2 mL/min    -   Column temperature: 35° C.    -   Detector: R.I. (refractometer)

(1) Liquid Chromatography Analysis Samples

About 0.1 g of sample were weighed followed by the addition of about 1 gof tetrahydrofuran (dehydrated, Wako Pure Chemical Industries, Ltd.,Japan) and about 0.02 g of internal standard in the form of bisphenol A(guaranteed reagent, Wako Pure Chemical Industries, Ltd., Japan) andmixing to uniformity to obtain solutions used as liquid chromatographyanalysis samples.

(2) Quantitative Analysis

Analyses were performed for each standard and quantitative analyses wereperformed on the analysis sample solutions based on the resultingcalibration curve.

3) Gas Chromatography

-   -   Apparatus: GC-2010, Shimadzu Corp., Japan    -   Column: DB-1 column, Agilent Technologies Corp., USA, length: 30        m, inner    -   diameter: 0.250 mm, film thickness: 1.00 μM    -   Column temperature: Held at 50° C. for 5 minutes followed by        increasing at the rate of 10° C./min to 200° C.; held at 200° C.        for 5 minutes followed by increasing at the rate of 10° C./min        to 300° C.    -   Detector: FID

(1) Gas Chromatography Analysis Samples

About 0.05 g of sample were weighed followed by the addition of about 1g of acetone (dehydrated, Wako Pure Chemical Industries, Ltd., Japan)and about 0.02 g of internal standard in the form of toluene(dehydrated, Wako Pure Chemical Industries, Ltd., Japan) and mixing touniformity to obtain solutions used as gas chromatography analysissamples.

(2) Quantitative Analysis

Analyses were performed for each standard and quantitative analyses wereperformed on the analysis sample solutions based on the resultingcalibration curve.

Example 1 Step (1-1): Production of Bis(3-methylbutyl) Carbonate

625 g (2.7 mol) of di-n-butyl tin oxide (Sankyo Organic Chemicals Co.,Ltd., Japan) and 2020 g (22.7 mol) of 3-methyl-1-butanol (Kuraray Co.,Ltd., Japan) were placed in a 5000 mL volumetric pear-shaped flask. Theflask was connected to an evaporator (R-144, Shibata Co., Ltd., Japan)to which was connected an oil bath (OBH-24, Masuda Corp., Japan)equipped with a temperature controller, a vacuum pump (G-50A, UlvacInc., Japan) and a vacuum controller (VC-10S, Okano Seisakusho Co.,Ltd.). The purge valve outlet of this evaporator was connected to a linecontaining nitrogen gas flowing at normal pressure. After closing thepurge valve of the evaporator to reduce pressure inside the system, thepurge valve was opened gradually to allow nitrogen to flow into thesystem and return to normal pressure. The oil bath temperature was setto about 145° C., the flask was immersed in the oil bath and rotation ofthe evaporator was started. After heating for about 40 minutes in thepresence of atmospheric pressure nitrogen with the purge valve of theevaporator left open, distillation of 3-methyl-1-butanol containingwater began. After maintaining in this state for 7 hours, the purgevalve was closed, pressure inside the system was gradually reduced, andexcess 3-methyl-1-butanol was distilled with the pressure inside thesystem at 74 to 35 kPa. After the fraction no longer appeared, the flaskwas taken out of the oil bath. After allowing the flask to cool to thevicinity of room temperature (25° C.), the flask was taken out of theoil bath, the purge valve was opened gradually and the pressure insidethe system was returned to atmospheric pressure. 1173 g of reactionliquid were obtained in the flask. Based on the results of ¹¹⁹Sn-, ¹H-and ¹³C-NMR analyses, 1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy)distannoxane was confirmed to have been obtained at a yield of 99% basedon di-n-butyl tin oxide. The same procedure was then repeated 12 timesto obtain a total of 10335 g of1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane.

Bis(3-methylbutyl)carbonate was produced in a continuous productionapparatus like that shown in FIG. 1.1,1,3,3-Tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane produced inthe manner described above was supplied at the rate of 4388 g/hr from atransfer line 4 into a column-type reaction vessel 102 packed with MetalGauze CY Packing (Sulzer Chemtech Ltd., Switzerland) and having an innerdiameter of 151 mm and effective length of 5040 mm, and3-methyl-1-butanol purified with a distillation column 101 was suppliedat the rate of 14953 g/hr from a transfer line 2. The liquid temperatureinside reaction vessel 102 was controlled to 160° C. by a heater and areboiler 112, and the pressure was adjusted to about 120 kPa-G with apressure control valve. The residence time in the reaction vessel wasabout 17 minutes. 3-methyl-1-butanol containing water at the rate of15037 g/hr from the top of the reaction vessel via a transfer line 6,and 3-methyl-1-butanol at the rate of 825 g/hr via feed line 1, werepumped to distillation column 101 packed with Metal Gauze CY Packing andprovided with a reboiler 111 and a condenser 121 to carry outdistillative purification. In the top of distillation column 101, afraction containing a high concentration of water was condensed bycondenser 121 and recovered from a recovery line 3. Purified3-methyl-1-butanol was pumped to column-type reaction vessel 102 viatransfer line 2 located in the lower portion of distillation column 101.An alkyl tin alkoxide catalyst composition containingdi-n-butyl-bis(3-methylbutyloxy) tin and1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane wasobtained from the lower portion of column-type reaction vessel 102, andsupplied to a thin film distillation apparatus 103 (KobelcoEco-Solutions Co., Ltd., Japan) via a transfer line 5. The3-methyl-1-butanol was distilled off in thin film distillation apparatus103 and returned to column-type reaction vessel 102 via a condenser 123,a transfer line 8 and transfer line 4. The alkyl tin alkoxide catalystcomposition was pumped from the lower portion of thin film distillationapparatus 103 via a transfer line 7 and supplied to an autoclave 104while adjusting the flow rate of di-n-butyl-bis(3-methylbutyloxy) tinand 1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane toabout 5130 g/hr. Carbon dioxide was supplied to the autoclave by atransfer line 9 at the rate of 973 g/hr, and the pressure inside theautoclave was maintained at 4 MPa-G. The temperature inside theautoclave was set to 120° C., the residence time was adjusted to about 4hours, and a reaction between the carbon dioxide and the alkyl tinalkoxide catalyst composition was carried out to obtain a reactionliquid containing bis(3-methylbutyl)carbonate. This reaction liquid wastransferred to a decarbonization tank 105 via a transfer line 10 and acontrol valve to remove residual carbon dioxide, and the carbon dioxidewas recovered from a transfer line 11. Subsequently, the reaction liquidwas transferred to a thin film distillation apparatus 106 (KobelcoEco-Solutions Co., Ltd., Japan) set to about 142° C. and about 0.5 kPavia a transfer line 12 and supplied while adjusting the flow rate of1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane to about4388 g/hr to obtain a fraction containing bis(3-methylbutyl)carbonate.On the other hand, the evaporation residue was circulated to column-typereaction vessel 102 via transfer line 13 and transfer line 4 whileadjusting the flow rate of1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane to about4388 g/hr. The fraction containing bis(3-methylbutyl)carbonate wassupplied to a distillation column 107 packed with Metal Gauze CY packingand equipped with a reboiler 117 and a condenser 127 via a condenser 126and a transfer line 14 at the rate of 959 g/hr followed by distillativepurification to obtain 99 wt % bis(3-methylbutyl)carbonate from arecovery line 16 at the rate of 944 g/hr. When the alkyl tin alkoxidecatalyst composition of a transfer line 13 was analyzed by ¹¹⁹Sn-, ¹H-and ¹³C-NMR analysis, it was found to contain1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane but notcontain di-n-butyl-bis(3-methylbutyloxy) tin. After carrying out theabove-mentioned continuous operation for about 240 hours, alkyl tinalkoxide catalyst composition was extracted from an extraction line 16at the rate of 18 g/hr, while1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane producedaccording to the above process was supplied from a feed line 17 at therate of 18 g/hr.

Step (1-2): Production of N,N′-hexanediyl-bis-carbamic AcidBis(3-methylbutyl) Ester

1537 g (7.6 mol) of bis(3-methylbutyl)carbonate obtained in step (1-2)and 220.8 g (1.9 mol) of hexamethylene diamine (Aldrich Corp., USA) wereplaced in a 5 L volumetric fourth-mouth flask, a stirrer was placed inthe flask, and a Dimroth condenser and three-way valve were attached tothe flask. After replacing the inside of the system with nitrogen, theflask was immersed in an oil bath (OBH-24, Masuda Corp., Japan) heatedto 80° C. followed by the addition of 18.3 g of sodium methoxide (25%methanol solution, Aldrich Corp., USA) with a syringe to start thereaction. Samples of the reaction liquid were suitably collected andsubjected to NMR analysis, and the reaction was terminated at the pointhexamethylene diamine was no longer detected.

The resulting solution was housed in an acidic sulfonic acid ionexchange resin (Amberlyst-15, spherical, Rohm and Haas Co., USA)adjusted by removing the moisture and supplied to a column warmed to 65°C. by an external jacket to neutralize the sodium methoxide in thesolution.

As a result of analyzing the solution by liquid chromatography, thesolution was found to contain 36.7% by weight ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester.

Step (1-3): Preparation of Composition

The solution obtained in step (1-2) and 2218 g of 2,4-di-tert-amylphenol(Tokyo Chemical Industry Co., Ltd., Japan) were mixed to obtain ahomogeneous solution. The solution was supplied to a moleculardistillation apparatus (MS-300, Sibata Scientific Technology, Ltd.,Japan) at the rate of 300 g/Hr and low boiling point components wereremoved at a temperature of about 130° C. and pressure of about 0.13 kPato obtain 1097 g of a distillate. As a result of analyzing by gaschromatography, the distillate was determined to be a solutioncontaining 69.2% by weight of bis(3-methylbutyl)carbonate and 29.0% byweight of 3-methyl-1-butanol. In addition, when the distillation residueobtained in the flask was analyzed by liquid chromatography, thedistillation residue was determined to contain 22.7% by weight ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester, and the yieldof N,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester based onhexamethylene diamine was 98%. The composition had a stoichiometricratio of N,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester and2,4-di-tert-amylphenol of 1:5.0. This composition was a liquid at 130°C., and after maintaining at 130° C. under a nitrogen atmosphere for 10days, the concentration of N,N′-hexanediyl-bis-carbamic acidbis(3-methylbutyl)ester was 22.6% by weight.

Example 2 Step (2-1): Production of Bis(3-methylbutyl) Carbonate

Bis(3-methylbutyl)carbonate was produced using the same method as Step(1-1) of Example 1.

Step (2-2): Production of N,N′-hexanediyl-bis-carbamic AcidBis(3-methylbutyl) Ester

A solution containing 31.3% by weight of N,N′-hexanediyl-bis-carbamicacid bis(3-methylbutyl)ester was obtained by carrying out the samemethod as step (1-2) of Example 1 with the exception of using 2039 g(10.1 mol) of the bis(3-methylbutyl) carbonate obtained in step (2-1),using 244 g (2.1 mol) of hexamethylene diamine, and using 20.3 g ofsodium methoxide (25% methanol solution).

Step (2-3): Production of Composition

1097 g of a distillate were obtained by carrying out the same method asstep (1-3) of Example 1 with the exception of using the solutionobtained in step (2-2) and 3560 g of 2-phenylphenol (Tokyo ChemicalIndustry Co., Ltd., Japan) instead of 2,4-di-tert-amylphenol. As aresult of analyzing by gas chromatography, the distillate was found tobe a solution containing 75.1% by weight of bis(3-methylbutyl) carbonateand 22.0% by weight of 3-methyl-1-butanol. In addition, as a result ofanalyzing by liquid chromatography, the distillation residue in theflask was found to contain 16.9% by weight ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl) ester, and theyield of N,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester basedon hexamethylene diamine was 97%. This solution was a composition inwhich the stoichiometric ratio of N,N′-hexanediyl-bis-carbamic acidbis(3-methylbutyl) ester and 2-phenylphenol was 1:9.9. This compositionwas a liquid at 130° C., and after maintaining at 130° C. under anitrogen atmosphere for 10 days, the concentration ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester was 16.9% byweight.

Example 3 Step (3-1): Production of Bis(3-methylbutyl)Carbonate

Bis(3-methylbutyl)carbonate was produced using the same method as Step(1-1) of Example 1.

Step (3-2): Production of N,N′-hexanediyl-bis-carbamic AcidBis(3-methylbutyl) Ester

A solution containing 28.4% by weight of N,N′-hexanediyl-bis-carbamicacid bis(3-methylbutyl)ester was obtained by carrying out the samemethod as step (1-2) of Example 1 with the exception of using 2630 g(13.0 mol) of the bis(3-methylbutyl) carbonate obtained in step (3-1),using 291 g (2.5 mol) of hexamethylene diamine, and using 24.1 g ofsodium methoxide (25% methanol solution).

Step (3-3): Production of Composition

2068 g of a distillate were obtained by carrying out the same method asstep (1-3) of Example 1 with the exception of using the solutionobtained in step (3-2) and 2401 g of 2,4-bis(α,α-dimethylbenzyl)phenol(Tokyo Chemical Industry Co., Ltd., Japan) instead of2,4-di-tert-amylphenol. As a result of analyzing by gas chromatography,the distillate was found to be a solution containing 79.3% by weight ofbis(3-methylbutyl)carbonate and 20.3% by weight of 3-methyl-1-butanol.In addition, as a result of analyzing by liquid chromatography, thedistillation residue in the flask was found to contain 25.5% by weightof N,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester, and theyield of N,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester basedon hexamethylene diamine was 97%. This solution was a composition inwhich the stoichiometric ratio of N,N′-hexanediyl-bis-carbamic acidbis(3-methylbutyl)ester and 2,4-bis(α,α-dimethylbenzyl)phenol was 1:3.0.This composition was a liquid at 130° C., and after maintaining at 130°C. under a nitrogen atmosphere for 10 days, the concentration ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester was 25.3% byweight.

Example 4 Step (4-1): Production of N,N′-hexanediyl-bis-carbamic AcidDimethyl Ester

A solution containing 33.4% by weight of N,N′-hexanediyl-bis-carbamicacid dimethyl ester was obtained by carrying out the same method as step(1-2) of Example 1 with the exception of using 1517 g (16.8 mol) ofdimethyl carbonate (Aldrich Corp., USA) instead ofbis(3-methylbutyl)carbonate, using 325 g (2.8 mol) of hexamethylenediamine, and using 5.4 g of sodium methoxide (25% methanol solution).

Step (4-2): Production of Composition

1326 g of a distillate were obtained by carrying out the same method asstep (1-3) of Example 1 with the exception of using the solutionobtained in step (4-1) and 6493 g of 2,6-xylenol (Tokyo ChemicalIndustry Co., Ltd., Japan) instead of 2,4-di-tert-amylphenol, and makingthe pressure inside the apparatus 13.1 kPa. As a result of analyzing bygas chromatography, the distillate was found to be a solution containing77.9% by weight of dimethyl carbonate and 12.8% by weight of methanol.In addition, as a result of analyzing by liquid chromatography, thedistillation residue obtained in the flask was found to contain 8.8% byweight of N,N′-hexanediyl-bis-carbamic acid dimethyl ester, and theyield of N,N′-hexanediyl-bis-carbamic acid dimethyl ester based onhexamethylene diamine was 95%. This solution was a composition in whichthe stoichiometric ratio of N,N′-hexanediyl-bis-carbamic acid dimethylester and 2,6-xylenol was 1:19.6. This composition was a liquid at 130°C., and after maintaining at 130° C. under a nitrogen atmosphere for 10days, the concentration of N,N′-hexanediyl-bis-carbamic acid dimethylester was 8.8% by weight.

Example 5 Step (5-1): Production of N,N′-hexanediyl-bis-carbamic AcidDimethyl Ester

A solution containing 44.6% by weight of N,N′-hexanediyl-bis-carbamicacid dimethyl ester was obtained by carrying out the same method as step(1-2) of Example 1 with the exception of using 1113 g (12.3 mol) ofdimethyl carbonate (Aldrich Corp., USA) instead ofbis(3-methylbutyl)carbonate, using 325 g (2.8 mol) of hexamethylenediamine, and using 5.4 g of sodium methoxide (25% methanol solution).

Step (5-2): Production of Composition

1086 g of a distillate were obtained by carrying out the same method asstep (1-3) of Example 1 with the exception of using the solutionobtained in step (5-1) and 13915 g of 2,4,6-trimethyphenol (AldrichCorp., USA) instead of 2,4-di-tert-amylphenol, and making the pressureinside the apparatus 13.1 kPa. As a result of analyzing by gaschromatography, the distillate was found to be a solution containing54.4% by weight of dimethyl carbonate and 15.7% by weight of methanol.In addition, as a result of analyzing by liquid chromatography, thedistillation residue obtained in the flask was found to contain 4.4% byweight of N,N′-hexanediyl-bis-carbamic acid dimethyl ester, and theyield of N,N′-hexanediyl-bis-carbamic acid dimethyl ester based onhexamethylene diamine was 96%. This solution was a composition in whichthe stoichiometric ratio of N,N′-hexanediyl-bis-carbamic acid dimethylester and 2,4,6-trimethylphenol was 1:37.1. This composition was aliquid at 130° C., and after maintaining at 130° C. under a nitrogenatmosphere for 10 days, the concentration ofN,N′-hexanediyl-bis-carbamic acid dimethyl ester was 4.3% by weight.

Example 6 Step (6-1): Production of N,N′-hexanediyl-bis-carbamic AcidDimethyl Ester

A solution containing 22.5% by weight of N,N′-hexanediyl-bis-carbamicacid dimethyl ester was obtained by carrying out the same method as step(1-2) of Example 1 with the exception of using 1987 g (22.0 mol) ofdimethyl carbonate instead of bis(3-methylbutyl)carbonate, using 256 g(2.2 mol) of hexamethylene diamine, and using 4.2 g of sodium methoxide(25% methanol solution).

Step (6-2): Production of Composition

2234 g of a distillate were obtained by carrying out the same method asstep (1-3) of Example 1 with the exception of using the solutionobtained in step (6-1) and 11092 g of 2-ethoxyphenol (Aldrich Corp.,USA) instead of 2,4-di-tert-amylphenol, and making the pressure insidethe apparatus 13.1 kPa. As a result of analyzing by gas chromatography,the distillate was found to be a solution containing 69.0% by weight ofdimethyl carbonate and 5.9% by weight of methanol. In addition, as aresult of analyzing by liquid chromatography, the distillation residueobtained in the flask was found to contain 4.5% by weight ofN,N′-hexanediyl-bis-carbamic acid dimethyl ester, and the yield ofN,N′-hexanediyl-bis-carbamic acid dimethyl ester based on hexamethylenediamine was 96%. This solution was a composition in which thestoichiometric ratio of N,N′-hexanediyl-bis-carbamic acid dimethyl esterand 2-ethoxyphenol was 1:36.1. This composition was a liquid at 130° C.,and after maintaining at 130° C. under a nitrogen atmosphere for 15days, the concentration of N,N′-hexanediyl-bis-carbamic acid dimethylester was 4.3% by weight.

Example 7 Step (7-1): Production of Dibutyl Carbonate

692 g (2.78 mol) of di-n-butyl tin oxide and 2000 g (27 mol) of1-butanol (Wako Pure Chemical Industries, Ltd., Japan) were placed in a3000 mL volumetric pear-shaped flask. The flask containing the mixturein the form of a white slurry was connected to an evaporator to whichwas connected an oil bath equipped with a temperature controller, avacuum pump and a vacuum controller. The purge valve outlet of thisevaporator was connected to a line containing nitrogen gas flowing atnormal pressure. After closing the purge valve of the evaporator toreduce pressure inside the system, the purge valve was opened graduallyto allow nitrogen to flow into the system and return to normal pressure.The oil bath temperature was set to about 126° C., the flask wasimmersed in the oil bath and rotation of the evaporator was started.After stirring and heating for about 30 minutes at normal pressure withthe purge valve of the evaporator left open, the mixture boiled anddistillation of a low boiling point component began. After maintainingin this state for 8 hours, the purge valve was closed, pressure insidethe system was gradually reduced, and remaining low boiling pointcomponent was distilled with the pressure inside the system at 76 to 54kPa. After the low boiling point component no longer appeared, the flaskwas taken out of the oil bath. The reaction liquid had become a clearliquid. Subsequently, the flask was taken out of the oil bath, the purgevalve was opened gradually and the pressure inside the system wasreturned to normal pressure. 952 g of reaction liquid were obtained inthe flask. Based on the results of ¹¹⁹Sn-, ¹H- and ¹³C-NMR analyses, theproduct 1,1,3,3-tetra-n-butyl-1,3-di(n-butyloxy) distannoxane wasobtained at a yield of 99% based on di-n-butyl tin oxide. The sameprocedure was then repeated 12 times to obtain a total of 11480 g of1,1,3,3-tetra-n-butyl-1,3-di(n-butyloxy) distannoxane.

Carbonic acid ester was produced in a continuous production apparatuslike that shown in FIG. 1. 1,1,3,3-tetra-n-butyl-1,3-di(n-butyloxy)distannoxane produced in the manner described above was supplied at therate of 4201 g/hr from a feed line 4 into a column-type reaction vessel102 packed with Mellapak 750Y Packing (Sulzer Chemtech Ltd.,Switzerland) and having an inner diameter of 151 mm and effective lengthof 5040 mm, and 1-butanol purified with a distillation column 101 wassupplied at the rate of 24717 g/hr from a feed line 2. The liquidtemperature inside reaction vessel 102 was controlled to 160° C. by aheater and a reboiler 112, and the pressure was adjusted to about 250kPa-G with a pressure control valve. The residence time in the reactionvessel was about 10 minutes. 1-Butanol containing water at the rate of24715 g/hr from the top of the reaction vessel via a transfer line 6,and 1-butanol at the rate of 824 g/hr via feed line 1, were pumped todistillation column 101 packed with Metal Gauze CY Packing (SulzerChemtech Ltd., Switzerland) and provided with reboiler 111 and condenser121 to carry out distillative purification. In the top of distillationcolumn 101, a fraction containing a high concentration of water wascondensed by condenser 121 and recovered from a transfer line 3.Purified 1-butanol was pumped via transfer line 2 located in the lowerportion of distillation column 101. An alkyl tin alkoxide catalystcomposition containing di-n-butyl-tin-di-n-butoxide and1,1,3,3-tetra-n-butyl-1,3-di(n-butyloxy) distannoxane was obtained fromthe lower portion of column-type reaction vessel 102, and supplied to athin film distillation apparatus 103 (Kobelco Eco-Solutions Co., Ltd.,Japan) via a transfer line 5. The 1-butanol was distilled off in thinfilm distillation apparatus 103 and returned to column-type reactionvessel 102 via condenser 123, transfer line 8 and transfer line 4. Thealkyl tin alkoxide catalyst composition was pumped from the lowerportion of thin film distillation apparatus 103 via transfer line 7 andsupplied to autoclave 104 while adjusting the flow rate of the activecomponents in the form of dibutyl tin dibutoxide and1,1,3,3-tetra-n-butyl-1,3-di(n-butyloxy) distannoxane to about 4812g/hr. Carbon dioxide was supplied to the autoclave by a feed line 9 atthe rate of 973 g/hr, and the pressure inside the autoclave wasmaintained at 4 MPa-G. The temperature inside the autoclave was set to120° C., the residence time was adjusted to about 4 hours, and areaction between the carbon dioxide and the alkyl tin alkoxide catalystcomposition was carried out to obtain a reaction liquid containingdibutyl carbonate. This reaction liquid was transferred todecarbonization tank 105 via transfer line 10 and a control valve toremove residual carbon dioxide, and the carbon dioxide was recoveredfrom transfer line 11. Subsequently, the reaction liquid was pumped tothin film distillation apparatus 106 (Kobelco Eco-Solutions Co., Ltd.,Japan) set to about 140° C. and about 1.4 kPa via transfer line 12 andsupplied while adjusting the flow rate of1,1,3,3-tetra-n-butyl-1,3-di(n-butyloxy) distannoxane to about 4201 g/hrto obtain a fraction containing dibutyl carbonate. On the other hand,the evaporation residue was circulated column-type reaction vessel 102via transfer line 13 and transfer line 4 while adjusting the flow rateof 1,1,3,3-tetra-n-butyl-1,3-di(n-butyloxy) distannoxane to about 4201g/hr. The fraction containing dibutyl carbonate was supplied todistillation column 107 packed with Metal Gauze CY packing (SulzerChemtech Ltd., Switzerland) and equipped with reboiler 117 and condenser127 via condenser 126 and transfer line 14 at the rate of 830 g/hrfollowed by distillative purification to obtain 99% by weightbis(3-methylbutyl)carbonate from transfer line 16 at the rate of 814g/hr. When the alkyl tin alkoxide catalyst composition of transfer line13 was analyzed by 119Sn-, ¹H- and ¹³C-NMR analysis, it was found tocontain 1,1,3,3-tetra-n-butyl-1,3-di(n-butyloxy) distannoxane but notcontain di-n-butyl tin-di-n-butoxide. After carrying out theabove-mentioned continuous operation for about 600 hours, alkyl tinalkoxide catalyst composition was extracted from extraction line 16 atthe rate of 16 g/hr, while 1,1,3,3-tetra-n-butyl-1,3-di(n-butyloxy)distannoxane produced according to the above process was supplied fromfeed line 17 at the rate of 16 g/hr.

Step (7-2): Production of N,N′-hexanediyl-bis-carbamic Acid DibutylEster

A solution containing 18.7% by weight of N,N′-hexanediyl-bis-carbamicacid dibutyl ester was obtained by carrying out the same method as step(1-2) of Example 1 with the exception of using 2760 g (15.8 mol) ofdibutyl carbonate obtained in step (7-1) instead ofbis(3-methylbutyl)carbonate, using 209 g (1.8 mol) of hexamethylenediamine, and using 10.4 g of sodium methoxide (25% methanol solution).

Step (7-3): Production of Composition

2241 g of a distillate were obtained by carrying out the same method asstep (1-3) of Example 1 with the exception of using the solutionobtained in step (7-2) and 3957 g of 2,6-dimethoxyphenol (Aldrich Corp.,USA) instead of 2,4-di-tert-amylphenol, and making the pressure insidethe apparatus 13.1 kPa. As a result of analyzing by gas chromatography,the distillate was found to be a solution containing 85.1% by weight ofdibutyl carbonate and 5.4% by weight of 1-butanol. In addition, as aresult of analyzing by liquid chromatography, the distillation residueobtained in the flask was found to contain 12.3% by weight ofN,N′-hexanediyl-bis-carbamic acid dibutyl ester, and the yield ofN,N′-hexanediyl-bis-carbamic acid dibutyl ester based on hexamethylenediamine was 95%. This solution was a composition in which thestoichiometric ratio of N,N′-hexanediyl-bis-carbamic acid dibutyl esterand 2,6-dimethoxyphenol was 1:14.1. This composition was a liquid at130° C., and after maintaining at 130° C. under a nitrogen atmospherefor 12 days, the concentration of N,N′-hexanediyl-bis-carbamic aciddibutyl ester was 12.3% by weight.

Example 8 Step (8-1): Production of Dibutyl Carbonate

Dibutyl carbonate was produced using the same method as step (7-1) ofExample 7.

Step (8-2): Production of N,N′-hexanediyl-bis-carbamic Acid DibutylEster

A solution containing 28.8% by weight of N,N′-hexanediyl-bis-carbamicacid dibutyl ester was obtained by carrying out the same method as step(1-2) of Example 1 with the exception of using 1821 g (10.5 mol) ofdibutyl carbonate obtained in step (8-1) instead ofbis(3-methylbutyl)carbonate, using 221 g (1.9 mol) of hexamethylenediamine, and using 11.0 g of sodium methoxide (25% methanol solution).

Step (8-3): Production of Composition

1488 g of a distillate were obtained by carrying out the same method asstep (1-3) of Example 1 with the exception of using the solutionobtained in step (8-2) and 8710 g of 4-nonylphenol (Aldrich Corp., USA)instead of 2,4-di-tert-amylphenol, and making the pressure inside theapparatus 13.1 kPa. As a result of analyzing by gas chromatography, thedistillate was found to be a solution containing 75.2% by weight ofdibutyl carbonate and 17.7% by weight of 1-butanol. In addition, as aresult of analyzing by liquid chromatography, the distillation residueobtained in the flask was found to contain 6.2% by weight ofN,N′-hexanediyl-bis-carbamic acid dibutyl ester, and the yield ofN,N′-hexanediyl-bis-carbamic acid dibutyl ester based on hexamethylenediamine was 83%. This solution was a composition in which thestoichiometric ratio of N,N′-hexanediyl-bis-carbamic acid dibutyl esterand 4-nonylphenol was 1:24.7. This composition was a liquid at 70° C.,and after maintaining at 70° C. under a nitrogen atmosphere for 70 days,the concentration of N,N′-hexanediyl-bis-carbamic acid dibutyl ester was6.2% by weight.

Example 9 Step (9-1): Production of Bis(3-methylbutyl) Carbonate

Bis(3-methylbutyl)carbonate was produced using the same method as step(1-1) of Example 1.

Step (9-2): Production of3-((3-methylbutyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicAcid (3-methyl butyl) Ester

2549 g (12.6 mol) of bis(3-methylbutyl)carbonate obtained in step (9-1)and 358 g (2.1 mol) of 3-aminomethyl-3,5,5-trimethylcyclohexylamine(Aldrich Corp., USA) were placed in a 5 L volumetric fourth-mouth flask,a stirrer was placed in the flask, and a Dimroth condenser and three-wayvalve were attached to the flask. After replacing the inside of thesystem with nitrogen, the flask was immersed in an oil bath (OBH-24,Masuda Corp., Japan) heated to 80° C. followed by the addition of 20.3 gof sodium methoxide (25% methanol solution) with a syringe to start thereaction. Samples of the reaction liquid were suitably collected andsubjected to NMR analysis, and the reaction was terminated at the point3-aminomethyl-3,5,5-trimethylcyclohexylamine was no longer detected.

The resulting solution was housed in a basic sulfonic acid ion exchangeresin (Amberlyst-15, spherical, Rohm and Haas Co., USA) adjusted byremoving the moisture and supplied to a column warmed to 65° C. by anexternal jacket to neutralize the sodium methoxide in the solution.

As a result of analyzing the solution by liquid chromatography, thesolution was found to contain 28.2% by weight of3-((3-methylbutypoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (3-methylbutyl)ester.

Step (9-3): Preparation of Composition

The solution obtained in step (9-2) and 4654 g of 2,4-di-tert-amylphenolwere mixed to obtain a homogeneous solution. The solution was suppliedto a molecular distillation apparatus (MS-300, Sibata ScientificTechnology, Ltd., Japan) at the rate of 300 g/Hr and low boiling pointcomponents were removed at a temperature of about 130° C. and pressureof about 0.13 kPa to obtain 2398 g of a distillate. As a result ofanalyzing by gas chromatography, the distillate was determined to be asolution containing 68.4% by weight of bis(3-methylbutyl)carbonate and14.3% by weight of 3-methyl-1-butanol. In addition, when thedistillation residue obtained in the flask was analyzed by liquidchromatography, the distillation residue was determined to contain 15.6%by weight of3-((3-methylbutyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (3-methylbutyl)ester and the yield of3-((3-methylbutyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (3-methylbutyl)ester based on3-aminomethyl-3,5,5-trimethylcyclohexylamine was 96%. The compositionhad a stoichiometric ratio of3-((3-methylbutyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (3-methylbutyl)ester and 2,4-di-tert-amylphenol of 1:9.1. Thiscomposition was a liquid at 80° C., and after maintaining at 80° C.under a nitrogen atmosphere for 100 days, the concentration of3-((3-methylbutyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (3-methylbutyl)ester was 15.5% by weight.

Example 10 Step (10-1): Production of Bis(3-methylbutyl) Carbonate

Bis(3-methylbutyl)carbonate was produced using the same method as step(1-1) of Example 1.

Step (10-2): Production of3-((3-methylbutyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicAcid (3-methylbutyl) Ester

A solution containing 33.0% by weight of3-((3-methylbutyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (3-methylbutyl)ester was obtained by carrying out the same methodas step (9-2) of Example 9 with the exception of using 2124 g (10.5 mol)of the bis(3-methylbutyl) carbonate obtained in step (10-1), using 358 g(2.1 mol) of 3-aminomethyl-3,5,5-trimethylcyclohexylamine, and using20.3 g of sodium methoxide (25% methanol solution).

Step (10-3): Production of Composition

1618 g of a distillate were obtained by carrying out the same method asstep (9-3) of Example 9 with the exception of using the solutionobtained in step (10-2) and 2625 g of 2,4-bis(α,α-dimethylbenzyl)phenolinstead of 2,4-di-tert-amylphenol. As a result of analyzing by gaschromatography, the distillate was found to be a solution containing76.1% by weight of bis(3-methylbutyl)carbonate and 21.5% by weight of3-methyl-1-butanol. In addition, as a result of analyzing by liquidchromatography, the distillation residue in the flask was found tocontain 23.2% by weight of3-((3-methylbutypoxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (3-methylbutyl)ester, and the yield of3-((3-methylbutyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (3-methylbutyl)ester based on3-aminomethyl-3,5,5-trimethylcyclohexylamine was 95%. This solution wasa composition in which the stoichiometric ratio of3-((3-methylbutyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (3-methylbutyl)ester and 2,4-bis(α,α-dimethylbenzyl)phenol was1:3.9. This composition was a liquid at 170° C., and after maintainingat 170° C. under a nitrogen atmosphere for 3 days, the concentration of3-((3-methylbutyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (3-methylbutyl)ester was 23.1% by weight.

Example 11 Step (11-1): Production of3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic AcidMethyl Ester

A solution containing 38.2% by weight of3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidmethyl ester was obtained by carrying out the same method as step (9-2)of Example 9 with the exception of using 1820 g (20.2 mol) of dimethylcarbonate instead of bis(3-methylbutyl)carbonate, using 545 g (3.2 mol)of 3-aminomethyl-3,5,5-trimethylcyclohexylamine, and using 12.3 g ofsodium methoxide (25% methanol solution).

Step (11-2): Production of Composition

2027 g of a distillate were obtained by carrying out the same method asstep (9-3) of Example 9 with the exception of using the solutionobtained in step (11-1) and 16270 g of 2,6-xylenol instead of2,4-di-tert-amylphenol, and making the pressure inside the apparatus13.1 kPa. As a result of analyzing by gas chromatography, the distillatewas found to be a solution containing 59.0% by weight of dimethylcarbonate and 9.6% by weight of methanol. In addition, as a result ofanalyzing by liquid chromatography, the distillation residue obtained inthe flask was found to contain 5.1% by weight of3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidmethyl ester, and the yield of3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidmethyl ester based on 3-aminomethyl-3,5,5-trimethylcyclohexylamine was95%. This solution was a composition in which the stoichiometric ratioof 3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid methyl ester and 2,6-xylenol was 1:43.3. This composition was aliquid at 130° C., and after maintaining at 130° C. under a nitrogenatmosphere for 10 days, the concentration of3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidmethyl ester was 5.1% by weight.

Example 12 Step (12-1): Production of3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic AcidMethyl Ester

A solution containing 46.7% by weight of3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidmethyl ester was obtained by carrying out the same method as step (9-2)of Example 9 with the exception of using 1214 g (13.4 mol) of dimethylcarbonate instead of bis(3-methylbutyl)carbonate, using 478 g (2.8 mol)of 3-aminomethyl-3,5,5-trimethylcyclohexylamine, and using 10.8 g ofsodium methoxide (25% methanol solution).

Step (12-2): Production of Composition

1427 g of a distillate were obtained by carrying out the same method asstep (9-3) of Example 9 with the exception of using the solutionobtained in step (12-1) and 11960 g of 2,4,6-trimethylphenol instead of2,4-di-tert-amylphenol, and making the pressure inside the apparatus13.1 kPa. As a result of analyzing by gas chromatography, the distillatewas found to be a solution containing 71.2% by weight of dimethylcarbonate and 17.1% by weight of methanol. In addition, as a result ofanalyzing by liquid chromatography, the distillation residue obtained inthe flask was found to contain 6.0% by weight of3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidmethyl ester, and the yield of3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidmethyl ester based on 3-aminomethyl-3,5,5-trimethylcyclohexylamine was94%. This solution was a composition in which the stoichiometric ratioof 3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid methyl ester and 2,4,6-trimethylphenol was 1:32.7. This compositionwas a liquid at 150° C., and after maintaining at 150° C. under anitrogen atmosphere for 2 days, the concentration of3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidmethyl ester was 6.0% by weight.

Example 13 Step (13-1): Production of Dibutyl Carbonate

Dibutyl carbonate was produced using the same method as step (7-1) ofExample 7.

Step (13-2): Production of3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic AcidButyl Ester

A solution containing 35.6% by weight of3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidbutyl ester was obtained by carrying out the same method as step (9-2)of Example 9 with the exception of using 2342 g (13.4 mol) of thedibutyl carbonate obtained in step (13-1), using 477 g (2.8 mol) of3-aminomethyl-3,5,5-trimethylcyclohexylamine, and using 20.3 g of sodiummethoxide (25% methanol solution).

Step (13-3): Production of Composition

1633 g of a distillate were obtained by carrying out the same method asstep (9-3) of Example 9 with the exception of using the solutionobtained in step (13-2) and 5805 g of 4-nonylphenol instead of2,4-di-tert-amylphenol. As a result of analyzing by gas chromatography,the distillate was found to be a solution containing 82.6% by weight ofdibutyl carbonate and 10.4% by weight of 1-butanol. In addition, as aresult of analyzing by liquid chromatography, the distillation residuein the flask was found to contain 14.1% by weight of3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidbutyl ester and the yield of3-((butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidbutyl ester based on 3-aminomethyl-3,5,5-trimethylcyclohexylamine was90%. This solution was a composition in which the stoichiometric ratioof 3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid butyl ester and 4-nonylphenol was 1:10.2. This composition was aliquid at 30° C., and after maintaining at 30° C. under a nitrogenatmosphere for 100 days, the concentration of3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidbutyl ester was 13.9% by weight.

Example 14 Step (14-1): Production of Dibutyl Carbonate

Dibutyl carbonate was produced using the same method as step (7-1) ofExample 7.

Step (14-2): Production of3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic AcidButyl Ester

A solution containing 28.3% by weight of3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidbutyl ester was obtained by carrying out the same method as step (9-2)of Example 9 with the exception of using 3403 g (19.5 mol) of thedibutyl carbonate obtained in step (14-1), using 528 g (3.1 mol) of3-aminomethyl-3,5,5-trimethylcyclohexylamine, and using 12.0 g of sodiummethoxide (25% methanol solution).

Step (14-3): Production of Composition

2814 g of a distillate were obtained by carrying out the same method asstep (9-3) of Example 9 with the exception of using the solutionobtained in step (14-2) and 9443 g of 2,4-dimethoxyphenol instead of2,4-di-tert-amylphenol. As a result of analyzing by gas chromatography,the distillate was found to be a solution containing 81.0% by weight ofdibutyl carbonate and 15.3% by weight of 1-butanol. In addition, as aresult of analyzing by liquid chromatography, the distillation residuein the flask was found to contain 10.3% by weight of3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidbutyl ester and the yield of3-((butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidbutyl ester based on 3-aminomethyl-3,5,5-trimethylcyclohexylamine was94.1%. This solution was a composition in which the stoichiometric ratioof 3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid butyl ester and 2,4-dimethoxyphenol was 1:20.8. This compositionwas a liquid at 30° C., and after maintaining at 30° C. under a nitrogenatmosphere for 90 days, the concentration of3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic acidbutyl ester was 10.0% by weight.

Example 15 Step (15-1): Production of Dibutyl Carbonate

Dibutyl carbonate was produced using the same method as step (7-1) ofExample 7.

Step (15-2): Production of Dibutyl-4,4′-methylene-dicyclohexylcarbamate

2305 g (13.2 mol) of dibutyl carbonate obtained in step (15-1) and 442 g(2.1 mol) of 4,4′-methylenebis(cyclohexylamine) (Aldrich Corp., USA)were placed in a 5 L volumetric fourth-mouth flask, a stirrer was placedin the flask, and a Dimroth condenser and three-way valve were attachedto the flask. After replacing the inside of the system with nitrogen,the flask was immersed in an oil bath heated to 80° C. followed by theaddition of 20.3 g of sodium methoxide (25% methanol solution) with asyringe to start the reaction. Samples of the reaction liquid weresuitably collected and subjected to NMR analysis, and the reaction wasterminated at the point 4,4′-methylenebis(cyclohexylamine) was no longerdetected.

The resulting solution was housed in a basic sulfonic acid ion exchangeresin (Amberlyst-15, spherical, Rohm and Haas Co., USA) adjusted byremoving the moisture and supplied to a column warmed to 65° C. by anexternal jacket to neutralize the sodium methoxide in the solution.

As a result of analyzing the solution by liquid chromatography, thesolution was found to contain 30.8% by weight ofdibutyl-4,4′-methylene-dicyclohexylcarbamate.

Step (15-3): Preparation of Composition

The solution obtained in step (15-2) and 6023 g of 2-tert-amylphenolwere mixed to obtain a homogeneous solution. The solution was suppliedto a molecular distillation apparatus (MS-300, Sibata ScientificTechnology, Ltd., Japan) at the rate of 300 g/Hr and low boiling pointcomponents were removed at a temperature of about 130° C. and pressureof about 0.13 kPa to obtain 1977 g of a distillate. As a result ofanalyzing by gas chromatography, the distillate was determined to be asolution containing 78.2% by weight of dibutyl carbonate and 15.2% byweight of 1-butanol. In addition, when the distillation residue obtainedin the flask was analyzed by liquid chromatography, the distillationresidue was determined to contain 12.4% by weight ofdibutyl-4,4′-methylene-dicyclohexylcarbamate and the yield ofdibutyl-4,4′-methylene-dicyclohexylcarbamate based on4,4′-methylenebis(cyclohexylamine) was 97%. The composition had astoichiometric ratio of dibutyl-4,4′-methylene-dicyclohexylcarbamate and2-tert-amylphenol of 1:17.6. This composition was a liquid at 30° C.,and after maintaining at 30° C. under a nitrogen atmosphere for 85 days,the concentration of dibutyl-4,4′-methylene-dicyclohexylcarbamate was12.2% by weight.

Example 16 Step (16-1): Production of Bis(3-methylbutyl)Carbonate

Bis(3-methylbutyl)carbonate was produced using the same method as step(1-1) of Example 1.

Step (16-2): Production ofBis(3-methylbutyl)-4,4′-methylene-dicyclohexyl Carbamate

A solution containing 34.7% by weight ofbis(3-methylbutyl)-4,4′-methylene-dicyclohexyl carbamate was obtained bycarrying out the same method as step (15-2) of Example 15 with theexception of using 2270 g (11.2 mol) of bis(3-methylbutyl)carbonateinstead of dibutyl carbonate, using 463 g (2.2 mol) of4,4′-methylenebis(cyclohexylamine) (Aldrich Corp., USA), and using 21.2g of sodium methoxide (25% methanol solution).

Step (16-3): Production of Composition

1775 g of a distillate were obtained by carrying out the same method asstep (15-3) of Example 15 with the exception of using the solutionobtained in step (16-2) and using 2476 g of 2,4-di-tert-amylphenolinstead of 2-tert-amylphenol. As a result of analyzing by gaschromatography, the distillate was found to be a solution containing75.7% by weight of bis(3-methylbutyl)carbonate and 16.9% by weight of3-methyl-1-butanol. In addition, as a result of analyzing by liquidchromatography, the distillation residue obtained in the flask was foundto contain 27.5% by weight ofbis(3-methylbutyl)-4,4′-methylene-dicyclohexyl carbamate, and the yieldof bis(3-methylbutyl)-4,4′-methylene-dicyclohexyl carbamate based on4,4′-methylenebis(cyclohexylamine) was 96%. This solution was acomposition in which the stoichiometric ratio ofbis(3-methylbutyl)-4,4′-methylene-dicyclohexyl carbamate and2,4-di-tert-amylphenol was 1:4.7. This composition was a liquid at 30°C., and after maintaining at 30° C. under a nitrogen atmosphere for 85days, the concentration ofbis(3-methylbutyl)-4,4′-methylene-dicyclohexyl carbamate was 27.2% byweight.

Example 17 Step (17-1): Production ofDimethyl-4,4′-methylene-dicyclohexyl Carbamate

A solution containing 48.3% by weight ofdimethyl-4,4′-methylene-dicyclohexyl carbamate was obtained by carryingout the same method as step (15-2) of Example 15 with the exception ofusing 1150 g (12.7 mol) of dimethyl carbonate instead of dibutylcarbonate, using 547 g (2.6 mol) of 4,4′-methylenebis(cyclohexylamine)(Aldrich Corp., USA), and using 25.1 g of sodium methoxide (25% methanolsolution).

Step (17-2): Production of Composition

1045 g of a distillate were obtained by carrying out the same method asstep (15-3) of Example 15 with the exception of using the solutionobtained in step (17-1) and using 5287 g of 2,4-diisopropylphenolinstead of 2-tert-amylphenol. As a result of analyzing by gaschromatography, the distillate was found to be a solution containing63.8% by weight of dimethyl carbonate and 15.1% by weight of methanol.In addition, as a result of analyzing by liquid chromatography, thedistillation residue obtained in the flask was found to contain 13.6% byweight of dimethyl-4,4′-methylene-dicyclohexyl carbamate, and the yieldof dimethyl-4,4′-methylene-dicyclohexyl carbamate based on4,4′-methylenebis(cyclohexylamine) was 95%. This solution was acomposition in which the stoichiometric ratio ofdimethyl-4,4′-methylene-dicyclohexyl carbamate and 2,4-diisopropylphenolwas 1:11.5. This composition was a liquid at 30° C., and aftermaintaining at 30° C. under a nitrogen atmosphere for 98 days, theconcentration of dimethyl-4,4′-methylene-dicyclohexyl carbamate was13.2% by weight.

Example 18 Step (18-1): Production ofDimethyl-4,4′-methylene-dicyclohexyl Carbamate

A solution containing 42.6% by weight ofdimethyl-4,4′-methylene-dicyclohexyl carbamate was obtained by carryingout the same method as step (15-2) of Example 15 with the exception ofusing 1625 g (18.0 mol) of dimethyl carbonate instead of dibutylcarbonate, using 631 g (3.0 mol) of 4,4′-methylenebis(cyclohexylamine)(Aldrich Corp., USA), and using 17.4 g of sodium methoxide (25% methanolsolution).

Step (18-2): Production of Composition

1699 g of a distillate were obtained by carrying out the same method asstep (15-3) of Example 15 with the exception of using the solutionobtained in step (18-1) and using 9600 g of 2,6-xylenol instead of2-tert-amylphenol. As a result of analyzing by gas chromatography, thedistillate was found to be a solution containing 62.6% by weight ofdimethyl carbonate and 10.9% by weight of methanol. In addition, as aresult of analyzing by liquid chromatography, the distillation residueobtained in the flask was found to contain 9.4% by weight ofdimethyl-4,4′-methylene-dicyclohexyl carbamate, and the yield ofdimethyl-4,4′-methylene-dicyclohexyl carbamate based on4,4′-methylenebis(cyclohexylamine) was 97%. This solution was acomposition in which the stoichiometric ratio ofdimethyl-4,4′-methylene-dicyclohexyl carbamate and 2,6-xylenol was1:25.7. This composition was a liquid at 130° C., and after maintainingat 130° C. under a nitrogen atmosphere for 3 days, the concentration ofdimethyl-4,4′-methylene-dicyclohexyl carbamate was 9.2% by weight.

Example 19 Step (19-1): Production of Bis(3-methylbutyl) Carbonate

Bis(3-methylbutyl)carbonate was produced using the same method as step(1-1) of Example 1.

Step (19-2): Production ofBis(3-methylbutyl)-4,4′-methylene-dicyclohexyl Carbamate

A solution containing 29.5% by weight ofbis(3-methylbutyl)-4,4′-methylene-dicyclohexyl carbamate was obtained bycarrying out the same method as step (15-2) of Example 15 with theexception of using 3010 g (14.9 mol) of bis(3-methylbutyl)carbonateobtained in step (16-1) instead of dibutyl carbonate, using 505 g (2.4mol) of 4,4′-methylenebis(cyclohexylamine), and using 23.1 g of sodiummethoxide (25% methanol solution).

Step (19-3): Production of Composition

2511 g of a distillate were obtained by carrying out the same method asstep (15-3) of Example 15 with the exception of using the solutionobtained in step (19-2) and using 5492 g of 2-phenylphenol instead of2-tert-amylphenol. As a result of analyzing by gas chromatography, thedistillate was found to be a solution containing 79.0% by weight ofbis(3-methylbutyl)carbonate and 16.1% by weight of 3-methyl-1-butanol.In addition, as a result of analyzing by liquid chromatography, thedistillation residue obtained in the flask was found to contain 15.0% byweight of bis(3-methylbutyl)-4,4′-methylene-dicyclohexyl carbamate, andthe yield of bis(3-methylbutyl)-4,4′-methylene-dicyclohexyl carbamatebased on 4,4′-methylenebis(cyclohexylamine) was 91.2%. This solution wasa composition in which the stoichiometric ratio ofbis(3-methylbutyl)-4,4′-methylene-dicyclohexyl carbamate and2-phenylphenol was 1:14.1. This composition was a liquid at 150° C., andafter maintaining at 150° C. under a nitrogen atmosphere for 1 day, theconcentration of bis(3-methylbutyl)-4,4′-methylene-dicyclohexylcarbamate was 13.3% by weight.

Example 20 Step (20-1): Production of Dibutyl Carbonate

Dibutyl carbonate was produced using the same method as step (7-1) ofExample 7.

Step (20-2): Production of Dibutyl-4,4′-methylene-dicyclohexyl Carbamate

A solution containing 33.0% by weight ofdibutyl-4,4′-methylene-dicyclohexyl carbamate was obtained by carryingout the same method as step (15-2) of Example 15 with the exception ofusing 3133 g (18.0 mol) of dibutyl carbonate obtained in step (20-1),using 652 g (3.1 mol) of 4,4′-methylenebis(cyclohexylamine), and using29.9 g of sodium methoxide (25% methanol solution).

Step (20-3): Production of Composition

2533 g of a distillate were obtained by carrying out the same method asstep (15-3) of Example 15 with the exception of using the solutionobtained in step (20-2) and using 4025 g of 4-tert-butylphenol insteadof 2-tert-amylphenol. As a result of analyzing by gas chromatography,the distillate was found to be a solution containing 78.8% by weight ofdibutyl carbonate and 17.4% by weight of 1-butanol. In addition, as aresult of analyzing by liquid chromatography, the distillation residueobtained in the flask was found to contain 21.4% by weight ofdibutyl-4,4′-methylene-dicyclohexyl carbamate, and the yield ofdibutyl-4,4′-methylene-dicyclohexyl carbamate based on4,4′-methylenebis(cyclohexylamine) was 87.4%. This solution was acomposition in which the stoichiometric ratio ofdibutyl-4,4′-methylene-dicyclohexyl carbamate and 4-tert-butylphenol was1:9.7. This composition was a liquid at 100° C., and after maintainingat 100° C. under a nitrogen atmosphere for 30 days, the concentration ofdibutyl-4,4′-methylene-dicyclohexyl carbamate was 21.0% by weight.

Example 21 Step (21-1): Production of Bis(3-methylbutyl) Carbonate

Bis(3-methylbutyl)carbonate was produced using the same method as step(1-1) of Example 1.

Step (21-2): Production of Toluene-2,4-dicarbamic AcidBis(3-methylbutyl) Ester

1529 g (7.6 mol) of bis(3-methylbutyl)carbonate obtained in step (21-1)and 257 g (2.1 mol) of 2,4-toluenediamine (Aldrich Corp., USA) wereplaced in a 5 L volumetric fourth-mouth flask, a stirrer was placed inthe flask, and a Dimroth condenser and three-way valve were attached tothe flask. After replacing the inside of the system with nitrogen, theflask was immersed in an oil bath heated to 80° C. followed by theaddition of 28.4 g of sodium methoxide (25% methanol solution) with asyringe to start the reaction. Samples of the reaction liquid weresuitably collected and subjected to NMR analysis, and the reaction wasterminated at the point 2,4-toluenediamine was no longer detected.

The resulting solution was housed in a basic sulfonic acid ion exchangeresin (Amberlyst-15, spherical, Rohm and Haas Co., USA) adjusted byremoving the moisture and supplied to a column warmed to 65° C. by anexternal jacket to neutralize the sodium methoxide in the solution.

As a result of analyzing the solution by liquid chromatography, thesolution was found to contain 39.8% by weight of toluene-2,4-dicarbamicacid bis(3-methylbutyl) ester.

Step (21-3): Preparation of Composition

The solution obtained in step (21-2) and 5411 g of 2,6-xylenol weremixed to obtain a homogeneous solution. The solution was supplied to amolecular distillation apparatus (MS-300, Sibata Scientific Technology,Ltd., Japan) at the rate of 300 g/Hr and low boiling point componentswere removed at a temperature of about 130° C. and pressure of about0.13 kPa to obtain 1461 g of a distillate. As a result of analyzing bygas chromatography, the distillate was determined to be a solutioncontaining 46.4% by weight of bis(3-methylbutyl)carbonate and 23.9% byweight of 3-methyl-1-butanol. In addition, when the distillation residueobtained in the flask was analyzed by liquid chromatography, thedistillation residue was determined to contain 12.3% by weight oftoluene-2,4-dicarbamic acid bis(3-methylbutyl)ester and the yield oftoluene-2,4-dicarbamic acid bis(3-methylbutyl)ester based on2,4-toluenediamine was 95%. The composition had a stoichiometric ratioof toluene-2,4-dicarbamic acid bis(3-methylbutyl)ester and2-tert-amylphenol of 1:20.3. This composition was a liquid at 120° C.,and after maintaining at 120° C. under a nitrogen atmosphere for 2 days,the concentration of toluene-2,4-dicarbamic acid bis(3-methylbutyl)esterwas 12.1% by weight.

Example 22 Step (22-1): Production of Toluene-2,4-dicarbamic AcidDimethyl Ester

A solution containing 33.1% by weight of toluene-2,4-dicarbamic aciddimethyl ester was obtained by carrying out the same method as step(21-2) of Example 21 with the exception of using 1422 g (15.8 mol) ofdimethyl carbonate instead of bis(3-methylbutyl)carbonate, using 305 g(2.5 mol) of 2,4-toluenediamine, and using 33.8 g of sodium methoxide(25% methanol solution).

Step (22-2): Production of Composition

1179 g of a distillate were obtained by carrying out the same method asstep (21-3) of Example 21 with the exception of using the solutionobtained in step (22-1) and using 5554 g of2,4-bis(α,α-dimethylbenzyl)phenol instead of 2,6-xylenol. As a result ofanalyzing by gas chromatography, the distillate was found to be asolution containing 81.2% by weight of dimethyl carbonate and 13.0% byweight of methanol. In addition, as a result of analyzing by liquidchromatography, the distillation residue obtained in the flask was foundto contain 9.4% by weight of toluene-2,4-dicarbamic acid dimethyl ester,and the yield of toluene-2,4-dicarbamic acid dimethyl ester based on2,4-toluenediamine was 96%. This solution was a composition in which thestoichiometric ratio of toluene-2,4-dicarbamic acid dimethyl ester and2,4-bis(α,α-dimethylbenzyl)phenol was 1:6.9. This composition was aliquid at 130° C., and after maintaining at 130° C. under a nitrogenatmosphere for 1 day, the concentration of toluene-2,4-dicarbamic aciddimethyl ester was 12.8% by weight.

Example 23 Step (23-1): Production of Bis(3-methylbutyl) Carbonate

Bis(3-methylbutyl)carbonate was produced using the same method as step(1-1) of Example 1.

Step (23-2): Production of N,N′-(4,4′-methanediyl-diphenyl)-biscarbamicAcid Bis(3-methylbutyl) Ester

2634 g (13.0 mol) of bis(3-methylbutyl)carbonate obtained in step (23-1)and 416.3 g (2.1 mol) of 4,4′-methylenedianiline (Aldrich Corp., USA)were placed in a 5 L volumetric fourth-mouth flask, a stirrer was placedin the flask, and a Dimroth condenser and three-way valve were attachedto the flask. After replacing the inside of the system with nitrogen,the flask was immersed in an oil bath heated to 80° C. followed by theaddition of 16.2 g of sodium methoxide (25% methanol solution) with asyringe to start the reaction. Samples of the reaction liquid weresuitably collected and subjected to NMR analysis, and the reaction wasterminated at the point 4,4′-methylenedianiline was no longer detected.

The resulting solution was housed in a basic sulfonic acid ion exchangeresin (Amberlyst-15, spherical, Rohm and Haas Co., USA) adjusted byremoving the moisture and supplied to a column warmed to 65° C. by anexternal jacket to neutralize the sodium methoxide in the solution.

As a result of analyzing the solution by liquid chromatography, thesolution was found to contain 28.6% by weight ofN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acidbis(3-methylbutyl)ester.

Step (23-3): Preparation of Composition

The solution obtained in step (23-2) and 2339 g of2,4-di-tert-amylphenol were mixed to obtain a homogeneous solution. Thesolution was supplied to a molecular distillation apparatus (MS-300,Sibata Scientific Technology, Ltd., Japan) at the rate of 300 g/Hr andlow boiling point components were removed at a temperature of about 130°C. and pressure of about 0.13 kPa to obtain 2341 g of a distillate. As aresult of analyzing by gas chromatography, the distillate was determinedto be a solution containing 74.5% by weight ofbis(3-methylbutyl)carbonate and 14.9% by weight of 3-methyl-1-butanol.In addition, when the distillation residue obtained in the flask wasanalyzed by liquid chromatography, the distillation residue wasdetermined to contain 28.6% by weight ofN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acidbis(3-methylbutyl)ester, and the yield ofN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acidbis(3-methylbutyl)ester based on 4,4′-methylenedianiline was 95%. Thecomposition had a stoichiometric ratio ofN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acidbis(3-methylbutyl)ester and 2,4-di-tert-amylphenol of 1:4.5. Thiscomposition was a liquid at 30° C., and after maintaining at 30° C.under a nitrogen atmosphere for 10 days, the concentration ofN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acidbis(3-methylbutyl)ester was 28.3% by weight.

Example 24 Step (24-1): Production of Dibutyl Carbonate

Dibutyl carbonate was produced using the same method as step (7-1) ofExample 7.

Step (24-2): Production of N,N′-(4,4′-methanediyl-diphenyl)-biscarbamicAcid Dibutyl Ester

A solution containing 36.9% by weightN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid dibutyl ester wasobtained by carrying out the same method as step (23-2) of Example 23with the exception of using 1622 g (9.3 mol) of dibutyl carbonateinstead of bis(3-methylbutyl)carbonate, using 377 g (1.9 mol) of4,4′-methylenedianiline, and using 11.0 g of sodium methoxide (25%methanol solution).

Step (24-3): Production of Composition

1430 g of a distillate were obtained by carrying out the same method asstep (23-3) of Example 23 with the exception of using the solutionobtained in step (24-2) and using 1988 g of 2,4,6-trimethylphenolinstead of 2,4-di-tert-amylphenol. As a result of analyzing by gaschromatography, the distillate was found to be a solution containing66.5% by weight of dibutyl carbonate and 18.8% by weight of 1-butanol.In addition, as a result of analyzing by liquid chromatography, thedistillation residue obtained in the flask was found to contain 28.8% byweight of N,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid dibutylester, and the yield of N,N′-(4,4′-methanediyl-diphenyl)-biscarbamicacid dibutyl ester based on 4,4′-methylenedianiline was 96%. Thissolution was a composition in which the stoichiometric ratio ofN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic acid dibutyl ester and2,4,6-trimethylphenol was 1:7.2. This composition was a liquid at 120°C., and after maintaining at 120° C. under a nitrogen atmosphere for 3days, the concentration of N,N′-(4,4′-methanediyl-diphenyl)-biscarbamicacid dibutyl ester was 28.2% by weight.

Example 25 Production of Hexamethylene Diisocyanate fromN,N′-hexanediyl-bis-carbamic Acid Bis(3-methylbutyl)Ester/2,4-di-tert-amylphenol Composition

58.7 g of dibutyl tin dilaurate (Wako Pure Chemical Industries, Ltd.,Japan) were added to the composition obtained in step (1-3) of Example 1to obtain a homogeneous solution.

A thermal decomposition reaction was carried out in a reaction apparatusas shown in FIG. 2 using this solution.

A thin film distillation apparatus 202 (Kobelco Eco-Solutions Co., Ltd.,Japan) having a heat-conducting surface area of 0.2 m² was heated to200° C. and the pressure within the thin film distillation apparatus wasset to about 1.3 kPa. The above solution was placed in a feed tank 201and supplied to the thin film distillation apparatus at the rate ofabout 980 g/hr via a line 21. A liquid component was extracted from aline 23 provided in the bottom of thin film distillation apparatus 202and returned to feed tank 201 via a line 24. A gaseous componentcontaining hexamethylene diisocyanate, 3-methyl-1-butanol and2,4-di-tert-amylphenol was extracted from a line 22 provided in theupper portion of thin film distillation apparatus 202. The gaseouscomponent was introduced into a distillation column 203 followed byseparation of the 3-methyl-1-butanol, and a portion of a high boilingpoint component was returned to feed tank 201 through a line 26 providedin the bottom of distillation column 203 via line 24. A gaseouscomponent containing hexamethylene diisocyanate and2,4-di-tert-amylphenol was extracted from a line 27 provided indistillation column 203, and introduced to a distillation column 204.Hexamethylene diisocyanate was separated in distillation column 204.After reacting for 13 hours, 294 g of a solution were recovered fromline 32. As a result of analyzing the solution by ¹H- and ¹³C-NMRanalysis, the solution was found to contain 99% by weight ofhexamethylene diisocyanate. The yield based on hexamethylene diamine was91.9%. In addition, there were no substances observed to be adhered tothe inside of the thin film evaporation apparatus.

Example 26 Production of Hexamethylene Diisocyanate fromN,N′-hexanediyl-bis-carbamic Acid Bis(3-methylbuty) Ester/2-phenylphenolComposition

301 g of a solution were recovered from line 32 by carrying out the samemethod as Example 25 with the exception of using the compositionobtained in step (2-3) of Example 2 instead of the composition obtainedin step (1-3) of Example 1, and using 64.2 g of dibutyl tin dilaurate(laboratory grade). As a result of analyzing the solution by ¹H- and¹³C-NMR analysis, the solution was found to contain 99% by weight ofhexamethylene diisocyanate. The yield based on hexamethylene diamine was85.2%. In addition, there were no substances observed to be adhered tothe inside of the thin film evaporation apparatus.

Example 27 Production of Hexamethylene Diisocyanate fromN,N′-hexanediyl-bis-carbamic Acid Bis(3-methylbuty)Ester/2,4-bis(α,α-dimethylbenzyl) Phenol Composition

378 g of a solution were recovered from line 32 by carrying out the samemethod as Example 25 with the exception of using the compositionobtained in step (3-3) of Example 3 instead of the composition obtainedin step (1-3) of Example 1, and using 76.4 g of dibutyl tin dilaurate(laboratory grade). As a result of analyzing the solution by ¹H- and¹³C-NMR analysis, the solution was found to contain 99% by weight ofhexamethylene diisocyanate. The yield based on hexamethylene diamine was90.0%. In addition, there were no substances observed to be adhered tothe inside of the thin film evaporation apparatus.

Example 28 Production of Hexamethylene Diisocyanate fromN,N′-hexanediyl-bis-carbamic Acid Bis(3-methylbuty) Ester/2,6-xylenolComposition Step (28-1): Production of N,N′-hexanediyl-bis-carbamic AcidDi(2,6-dimethylphenyl) Ester by Transesterification

A transesterification reaction was carried out in a reaction apparatusas shown in FIG. 3.

83.9 g of dibutyl tin dilaurate were added to the composition obtainedin step (4-3) of Example 4 to obtain a homogeneous solution. Thesolution was introduced into a feed tank 401. A thin film distillationapparatus 402 (Kobelco Eco-Solutions Co., Ltd., Japan) having aheat-conducting surface area of 0.2 m² was heated to 240° C. and theinside of the thin film distillation apparatus was replaced withnitrogen at atmospheric pressure. The solution was supplied to the thinfilm distillation apparatus at the rate of about 1200 g/hr via a line41. A mixed gas containing 3-methyl-1-butanol and 2,6-xylenol wasextracted from a line 45 provided in the upper portion of the thin filmdistillation apparatus 402 and supplied to a distillation column 403packed with Metal Gauze CY Packing (Sulzer Chemtech Ltd., Switzerland).3-Methyl-1-butanol and 2,6-xylenol were separated in distillation column403, and the 2,6-xylenol was returned to the upper portion of thin filmdistillation apparatus 402 from a line 46 provided in the bottom ofdistillation column 403. A reaction liquid was extracted from a line 42provided in the bottom of the thin film distillation apparatus 402 andreturned to feed tank 401 via a line 43.

After carrying out this step for 62 hours, a reaction liquid wasextracted from a line 44. 6926 g of reaction liquid were extracted and166 g of a solution were recovered from a line 47 provided in the upperportion of a distillation column 203.

When the extracted reaction liquid was analyzed by liquidchromatography, the reaction liquid was found to contain 15.2% by weightof N,N′-hexanediyl-bis-carbamic acid bis(2,6-dimethylphenyl) ester. Inaddition, when the solution recovered from line 47 was analyzed by ¹H-and ¹³C-NMR analysis, the solution was found to contain 98% by weight ofmethanol.

Step (28-2): Production of Hexamethylene Diisocyanate by ThermalDecomposition of N,N′-hexanediyl-bis-carbamic AcidDi(2,6-dimethylphenyl) Ester

A thermal decomposition reaction was carried out in a reaction apparatusas shown in FIG. 2.

A thin film distillation apparatus 202 (Kobelco Eco-Solutions Co., Ltd.,Japan) having a heat-conducting surface area of 0.2 m² was heated to200° C. and the pressure within the thin film distillation apparatus wasset to about 1.3 kPa. The solution obtained in step (28-1) wasintroduced into a feed tank 201 and supplied to the thin filmdistillation apparatus at the rate of about 680 g/hr via line 21. Aliquid component was extracted from line 23 provided in the bottom ofthin film distillation apparatus 202 and returned to feed tank 201 vialine 24. A gaseous component containing hexamethylene diisocyanate and2,6-dimethylphenol was extracted from line 22 provided in the upperportion of thin film distillation apparatus 202. The gaseous componentwas introduced into distillation column 203 followed by separation ofthe hexamethylene diisocyanate and 2,6-dimethylphenol, the2,6-dimethylphenol was extracted from a line 25 after passing throughthe top of distillation column 203, and a gaseous component containinghexamethylene diisocyanate was extracted from a line 27 provided indistillation column 203. On the other hand, a high boiling pointcomponent was extracted from line 26 provided in the bottom of thedistillation column, and a portion thereof was returned to feed tank 201via line 24. The gaseous component containing hexamethylene diisocyanateextracted from line 27 was transferred to distillation column 204, andthe hexamethylene diisocyanate was separated by distillation indistillation column 204. A high boiling point component was extractedfrom line 31 provided in distillation column 204, and a portion thereofwas returned to feed tank 201 via line 24. On the other hand, a gaseouscomponent was extracted from line 30, and hexamethylene diisocyanate wasextracted from line 32 after passing through a condenser. After reactingfor 11 hours, 416 g of a solution containing 99% by weight ofhexamethylene diisocyanate were recovered from line 32. The yield basedon hexamethylene diamine was 88.4%.

Example 29 Production of Hexamethylene Diisocyanate UsingN,N′-hexanediyl-bis-carbamic Acid Dimethyl Ester/2,4,6-trimethylphenolComposition

84.9 g of dibutyl tin dilaurate were added to the composition obtainedin step (5-2) to obtain a homogeneous solution.

A thermal decomposition reaction was carried out in a reaction apparatusas shown in FIG. 4 using this solution.

A thin film distillation apparatus 502 (Kobelco Eco-Solutions Co., Ltd.,Japan) having a heat-conducting surface area of 0.2 m² was heated to200° C. and the pressure within the thin film distillation apparatus wasset to about 1.3 kPa. The above solution was placed in a feed tank 501and supplied to the thin film distillation apparatus at the rate ofabout 980 g/hr via a line 51. A liquid component was extracted from aline 53 provided in the bottom of thin film distillation apparatus 502and returned to feed tank 501 via a line 54. A gaseous componentcontaining hexamethylene diisocyanate, methanol and2,4,6-trimethylphenol was extracted from a line 52 provided in the upperportion of thin film distillation apparatus 502. The gaseous componentwas introduced into a distillation column 503 followed by separation ofthe methanol, and a portion of a high boiling point component wasreturned to feed tank 501 through a line 56 provided in the bottom ofdistillation column 503 via line 54. A gaseous component containinghexamethylene diisocyanate and 2,4,6-trimethylphenol was extracted froma line 57 provided in distillation column 503, and introduced to adistillation column 504. 2,4,6-trimethylphenol was separated indistillation column 504 and recovered from a line 62. A gaseouscomponent containing hexamethylene diisocyanate was extracted from aline 64 provided in distillation column 504 and introduced into adistillation column 505. The hexamethylene diisocyanate was separated bydistillation in distillation column 505 and recovered from a line 67.After reacting for 13 hours, 430 g of a solution were recovered fromline 67. As a result of analyzing the solution by ¹H- and ¹³C-NMRanalysis, the solution was found to contain 99% by weight ofhexamethylene diisocyanate. The yield based on hexamethylene diamine was91.2%. In addition, there were no substances observed to be adhered tothe inside of the thin film evaporation apparatus.

Example 30 Production of Hexamethylene Diisocyanate UsingN,N′-hexanediyl-bis-carbamic Acid Dimethyl Ester/2-ethoxyphenolComposition

330 g of a solution were recovered from line 67 by carrying out the samemethod as Example 29 with the exception of using the compositionobtained in step (6-2) instead of the composition obtained in step(5-2), and using 66.7 g of dibutyl tin dilaurate. As a result ofanalyzing the solution by ¹H- and ¹³C-NMR analysis, the solution wasfound to contain 99% by weight of hexamethylene diisocyanate. The yieldbased on hexamethylene diamine was 89.3%. In addition, there were nosubstances observed to be adhered to the inside of the thin filmevaporation apparatus.

Example 31 Production of Hexamethylene Diisocyanate fromN,N′-hexanediyl-bis-carbamic Acid Dibutyl Ester/2,6-dimethoxyphenolComposition Step (31-1): Production of N,N′-hexanediyl-bis-carbamic AcidBis(2,6-dimethoxyphenyl) Ester by Transesterification

A transesterification reaction was carried out in a reaction apparatusas shown in FIG. 3.

4088 g of a reaction liquid were recovered from line 44 by carrying outthe same method as step (28-1) of Example 28 with the exception of usingthe composition obtained in step (7-3) of Example 7 instead of thecomposition obtained in step (4-3) of Example 4, and using 54.0 g ofdibutyl tin dilaurate. As a result of analyzing the reaction liquid byliquid chromatography, the reaction liquid was found to contain 19.1% byweight of N,N′-hexanediyl-bis-carbamic acid bis(2,6-dimethoxyphenol)ester. In addition, as a result of analyzing the solution recovered fromline 47 by ¹H- and ¹³C-NMR analysis, the solution was found to contain96% by weight of butanol.

Step (31-2): Production of Hexamethylene Diisocyanate by ThermalDecomposition of N,N′-hexanediyl-bis-carbamic AcidBis(2,6-dimethoxyphenyl) Ester

267 g of a solution containing 99% by weight of hexamethylenediisocyanate were recovered from line 32 by carrying out the same methodas step (28-2) of Example 28 with the exception of using the solutionobtained in step (31-1) instead of the solution obtained in step (28-1).The yield based on hexamethylene diamine was 88.4%.

Example 32 Production of Hexamethylene Diisocyanate fromN,N′-hexanediyl-bis-carbamic Acid Dibutyl Ester/4-nonylphenolComposition

257 g of a solution were recovered from line 32 by carrying out the samemethod as Example 25 with the exception of using the compositionobtained in step (8-3) of Example 8 instead of the composition obtainedin step (1-3) of Example 1, and using 56.8 g of dibutyl tin dilaurate(laboratory grade). As a result of analyzing the solution by ¹H- and¹³C-NMR analysis, the solution was found to contain 99% by weight ofhexamethylene diisocyanate. The yield based on hexamethylene diamine was80.4%. In addition, there were no substances observed to be adhered tothe inside of the thin film evaporation apparatus.

Example 33 Production of Isophorone Diisocyanate from3-((3-methylbutyl)oxycarbonyl-amino-methyl)-3,5,5-trimethylcyclohexylcarbamicAcid (3-methylbutyl) Ester/2,4-di-tert-amylphenol Composition

390 g of a solution were recovered from line 32 by carrying out the samemethod as Example 25 with the exception of using the compositionobtained in step (9-3) of Example 9 instead of the composition obtainedin step (1-3) of Example 1, and using 62.7 g of dibutyl tin dilaurate(laboratory grade). As a result of analyzing the solution by ¹H- and¹³C-NMR analysis, the solution was found to contain 99% by weight ofisophorone diisocyanate. The yield based on3-aminomethyl-3,5,5-trimethylcyclohexylamine was 85.1%. In addition,there were no substances observed to be adhered to the inside of thethin film evaporation apparatus.

Example 34 Production of Isophorone Diisocyanate from3-((3-methylbutyl)oxycarbonyl-amino-methyl)-3,5,5-trimethylcyclohexylcarbamicAcid (3-methylbutyl) Ester/2,4-bis(α,α-dimethylbenzyl) PhenolComposition

392 g of a solution were recovered from line 32 by carrying out the samemethod as Example 25 with the exception of using the compositionobtained in step (10-3) of Example 10 instead of the compositionobtained in step (1-3) of Example 1, and using 62.6 g of dibutyl tindilaurate (laboratory grade). As a result of analyzing the solution by¹H- and ¹³C-NMR analysis, the solution was found to contain 99% byweight of isophorone diisocyanate. The yield based on3-aminomethyl-3,5,5-trimethylcyclohexylamine was 84.0%. In addition,there were no substances observed to be adhered to the inside of thethin film evaporation apparatus.

Example 35 Production of Isophorone Diisocyanate from3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic AcidMethyl Ester/2,6-Dimethylphenol Composition

588 g of a solution were recovered from line 67 by carrying out the samemethod as Example 29 with the exception of using the compositionobtained in step (11-2) instead of the composition obtained in step(5-2), and using 96.1 g of dibutyl tin dilaurate. As a result ofanalyzing the solution by ¹H- and ¹³C-NMR analysis, the solution wasfound to contain 99% by weight of isophorone diisocyanate. The yieldbased on 3-aminomethyl-3,5,5-trimethylcyclohexylamine was 82.7%. Inaddition, there were no substances observed to be adhered to the insideof the thin film evaporation apparatus.

Example 36 Production of Isophorone Diisocyanate from3-(methyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic AcidMethyl Ester/2,4,6-trimethylphenol Composition Step (36-1): Productionof3-((2,4,6-trimethylphenyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicAcid (2,4,6-trimethylphenyl) Ester by Transesterification

A transesterification reaction was carried out in a reaction apparatusas shown in FIG. 3.

12410 g of a reaction liquid were recovered from line 44 by carrying outthe same method as step (28-1) of Example 28 with the exception of usingthe composition obtained in step (12-2) of Example 12 instead of thecomposition obtained in step (4-3) of Example 4, and using 83.2 g ofdibutyl tin dilaurate. As a result of analyzing the reaction liquid byliquid chromatography, the reaction liquid was found to contain 10.1% byweight of3-((2,4,6-trimethylphenyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (2,4,6-trimethylphenyl) ester. In addition, as a result ofanalyzing the solution recovered from line 47 by ¹H— and ¹³C-NMRanalysis, the solution was found to contain 98% by weight of methanol.

Step (36-2): Production of Isophorone Diisocyanate by ThermalDecomposition of3-((2,4,6-trimethylphenyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicAcid (2,4,6-trimethylphenyl) Ester

544 g of a solution containing 99% by weight of isophorone diisocyanatewere recovered from line 32 by carrying out the same method as step(28-2) of Example 28 with the exception of using the solution obtainedin step (36-1) instead of the solution obtained in step (28-1). Theyield based on 3-amino-methyl-3,5,5-trimethylcyclohexylamine was 87.5%.

Example 37 Production of Isophorone Diisocyanate from3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic AcidButyl Ester/4-nonylphenol Composition Step (37-1): Production of3-((4-nonylphenyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicAcid (4-nonylphenyl) Ester by Transesterification

A transesterification reaction was carried out in a reaction apparatusas shown in FIG. 3.

83.2 g of dibutyl tin dilaurate were added to the composition obtainedin step (13-3) of Example 13 to obtain a homogeneous solution. Thesolution was placed in feed tank 401. Thin film distillation apparatus402 (Kobelco Eco-Solutions Co., Ltd., Japan) having a heat-conductingsurface area of 0.2 m² was heated to 240° C. and the inside of the thinfilm distillation apparatus was replaced with nitrogen at atmosphericpressure. The solution was supplied to the thin film distillationapparatus at the rate of about 1200 g/hr via feed line 41. A mixed gascontaining 1-butanol and 4-nonylphenol was extracted from line 45provided in the upper portion of the thin film distillation apparatus402 and supplied to distillation column 403 packed with Metal Gauze CYPacking (Sulzer Chemtech Ltd., Switzerland). 1-Butanol and 4-nonylphenolwere separated in distillation column 403, and the 4-nonylphenol wasreturned to the upper portion of thin film distillation apparatus 402from line 46 provided in the bottom of distillation column 403. Areaction liquid was extracted from line 42 provided in the bottom of thethin film distillation apparatus 402 and returned to feed tank 401 vialine 43.

After carrying out this step for 62 hours, a reaction liquid wasextracted from line 44. 6419 g of reaction liquid were extracted and 575g of a solution were recovered from line 47 provided in the upperportion of a distillation column 403.

When the extracted reaction liquid was analyzed by liquidchromatography, the reaction liquid was found to contain 24.5% by weightof3-((4-nonylphenyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (4-nonylphenyl) ester. In addition, when the solution recoveredfrom line 47 was analyzed by ¹H- and ¹³C-NMR analysis, the solution wasfound to contain 98% by weight of 1-butanol.

Step (37-2): Production of Isophorone Diisocyanate by ThermalDecomposition of3-((4-nonylphenyl)oxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicAcid (4-nonylphenyl) Ester

A thermal decomposition reaction was carried out in a reaction apparatusas shown in FIG. 5.

A thin film distillation apparatus 702 (Kobelco Eco-Solutions Co., Ltd.,Japan) having a heat-conducting surface area of 0.2 m² was heated to200° C. and the pressure within the thin film distillation apparatus wasset to about 1.3 kPa. The solution obtained in step (37-2) was placed ina feed tank 701 and supplied to the thin film distillation apparatus atthe rate of about 980 g/hr via a line 71. A liquid component wasextracted from a line 73 provided in the bottom of thin filmdistillation apparatus 702 and returned to feed tank 701 via a line 74.A gaseous component containing isophorone diisocyanate and 4-nonylphenolwas extracted from a line 72 provided in the upper portion of thin filmdistillation apparatus 702. The gaseous component was introduced into adistillation column 703, the isophorone diisocyanate and 4-nonylphenolwere separated, and a portion of the 4-nonylphenol was returned to feedtank 701 through line 74 via a line 76 provided in the bottom ofdistillation column 703. After reacting for 13 hours, 484 g of asolution were recovered from a line 75. As a result of analyzing by ¹H-and ¹³C-NMR analysis, the solution was found to contain 99% by weight ofisophorone diisocyanate. The yield based on3-aminomethyl-3,5,5-trimethylcyclohexylamine was 77.8%.

Example 38 Production of Isophorone Diisocyanate from3-(butyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamic AcidButyl Ester/2,6-dimethoxyphenol Composition Step (38-1): Production of3-((2,6-dimethoxyphenyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicAcid (2,6-dimethoxyphenyl) Ester by Transesterification

A transesterification reaction was carried out in a reaction apparatusas shown in FIG. 3.

10121 g of a reaction liquid were recovered from line 44 by carrying outthe same method as step (28-1) of Example 28 with the exception of usingthe composition obtained in step (14-3) of Example 14 instead of thecomposition obtained in step (4-3) of Example 4, and using 92.1 g ofdibutyl tin dilaurate. As a result of analyzing the reaction liquid byliquid chromatography, the reaction liquid was found to contain 14.7% byweight of3-((2,6-dimethoxyphenyloxycarbonylamino-methyl)-3,5,5-trimethylcyclohexylcarbamicacid (2,6-dimethoxyphenyl) ester produced by the transesterificationreaction. In addition, as a result of analyzing the solution recoveredfrom line 27 by ¹H- and ¹³C-NMR analysis, the solution was found tocontain 98% by weight of 1-butanol.

Step (38-2): Production of Isophorone Diisocyanate by ThermalDecomposition of3-((2,6-dimethoxyphenyloxycarbonylaminomethyl)-3,5,5-trimethylcyclohexylcarbamicAcid (2,6-dimethoxyphenyl) Ester

579 g of a solution containing 99% by weight of isophorone diisocyanatewere recovered from line 32 by carrying out the same method as step(28-2) of Example 28 with the exception of using the solution obtainedin step (38-1) instead of the solution obtained in step (28-1). Theyield based on 3-aminomethyl-3,5,5-trimethylcyclohexylamine was 84.0%.

Example 39 Production of 4,4′-methylenebis(cyclohexyl isocyanate) UsingDibutyl-4,4′-methylene-dicyclohexyl Carbamate/2-tert-amylphenolComposition

481 g of a solution were recovered from line 67 by carrying out the samemethod as Example 29 with the exception of using the compositionobtained in step (15-3) instead of the composition obtained in step(5-2), and using 64.4 g of dibutyl tin dilaurate. As a result ofanalyzing the solution by ¹H- and ¹³C-NMR analysis, the solution wasfound to contain 99% by weight of4,4′-methylenebis(cyclohexyldiisocyanate).

The yield based on 4,4′-methylenebis(cyclohexylamine) was 87.3%. Inaddition, there were no substances observed to be adhered to the insideof the thin film evaporation apparatus following the reaction.

Example 40 Production of 4,4′-methylenebis(cyclohexyl isocyanate) UsingBis(3-methylbutyl)-4,4′-methylene-dicyclohexylCarbamate/2,4-di-tert-amylphenol Composition

498 g of a solution were recovered from line 67 by carrying out the samemethod as Example 29 with the exception of using the compositionobtained in step (16-3) instead of the composition obtained in step(5-2), and using 66.7 g of dibutyl tin dilaurate. As a result ofanalyzing the solution by ¹H- and ¹³C-NMR analysis, the solution wasfound to contain 99% by weight of4,4′-methylenebis(cyclohexyldiisocyanate). The yield based on4,4′-methylenebis(cyclohexylamine) was 86.4%. In addition, there were nosubstances observed to be adhered to the inside of the thin filmevaporation apparatus following the reaction.

Example 41 Production of 4,4′-methylenebis(cyclohexyl isocyanate) UsingDimethyl-4,4′-methylene-dicyclohexyl Carbamate/2,6-diisopropylphenolComposition

577 g of a solution were recovered from line 67 by carrying out the samemethod as Example 29 with the exception of using the compositionobtained in step (17-2) instead of the composition obtained in step(5-2), and using 78.1 g of dibutyl tin dilaurate. As a result ofanalyzing the solution by ¹H- and ¹³C-NMR analysis, the solution wasfound to contain 99% by weight of4,4′-methylenebis(cyclohexyldiisocyanate). The yield based on4,4′-methylenebis(cyclohexylamine) was 84.6%. In addition, there were nosubstances observed to be adhered to the inside of the thin filmevaporation apparatus following the reaction.

Example 42 Production of 4,4′-methylenebis(cyclohexylisocyanate) fromDimethyl-4,4′-methylene-dicyclohexyl Carbamate/2,6-dimethylphenolComposition Step (42-1): Production ofBis(2,6-dimethylphenyl)-4,4′-methylenedicyclohexyl Carbamate byTransesterification

A transesterification reaction was carried out in a reaction apparatusas shown in FIG. 3.

5832 g of a reaction liquid were recovered from line 44 by carrying outthe same method as step (28-1) of Example 28 with the exception of usingthe composition obtained in step (18-2) of Example 18 instead of thecomposition obtained in step (4-3) of Example 4, and using 78.1 g ofdibutyl tin dilaurate. As a result of analyzing the reaction liquid byliquid chromatography, the reaction liquid was found to contain 25.2% byweight of bis(2,6-dimethylphenyl)-4,4′-methylene-dicyclohexyl carbamate.In addition, as a result of analyzing the solution recovered from line47 by ¹H- and ¹³C-NMR analysis, the solution was found to contain 96% byweight of methanol.

Step (42-2): Production of Hexamethylene Diisocyanate by ThermalDecomposition of bis(2,6-dimethylphenyl)-4,4′-methylene-dicyclohexylCarbamate

603 g of a solution containing 99% by weight of 4,4′-methylenebis(cyclohexyldiisocyanate) were recovered from line 32 by carrying out thesame method as step (28-2) of Example 28 with the exception of using thesolution obtained in step (42-1) instead of the solution obtained instep (28-1). The yield based on 4,4′-methylenebis(cyclohexylamine) was88.5%.

Example 43 Production of 4,4′-methylenebis(cyclohexylisocyanate) fromBis(3-methylbutyl)-4,4′-methylene-dicyclohexyl Carbamate/2-phenylphenolComposition Step (43-1): Production ofBis(2-phenylphenyl)-4,4′-methylenedicyclohexyl Carbamate byTransesterification

A transesterification reaction was carried out in a reaction apparatusas shown in FIG. 3.

6091 g of a reaction liquid were recovered from line 44 by carrying outthe same method as step (28-1) of Example 28 with the exception of usingthe composition obtained in step (19-3) of Example 19 instead of thecomposition obtained in step (4-3) of Example 4, and using 72.8 g ofdibutyl tin dilaurate. As a result of analyzing the reaction liquid byliquid chromatography, the reaction liquid was found to contain 25.2% byweight of bis(2-phenylphenyl)-4,4′-methylene-dicyclohexyl carbamate. Inaddition, as a result of analyzing the solution recovered from line 47by ¹H- and ¹³C-NMR analysis, the solution was found to contain 96% byweight of 3-methyl-1-butanol.

Step (43-2): Production of Hexamethylene Diisocyanate by ThermalDecomposition of bis(2-phenylphenyl)-4,4′-methylene-dicyclohexylCarbamate

517 g of a solution containing 99% by weight of 4,4′-methylenebis(cyclohexyldiisocyanate) were recovered from line 32 by carrying out thesame method as step (28-2) of Example 28 with the exception of using thesolution obtained in step (43-1) instead of the solution obtained instep (28-1). The yield based on 4,4′-methylenebis(cyclohexylamine) was82.0%.

Example 44 Production of 4,4′-methylenebis(cyclohexyl isocyanate) UsingDibutyl-4,4′-methylene-dicyclohexyl Carbamate/4-tert-butylphenolComposition

630 g of a solution were recovered from line 67 by carrying out the samemethod as Example 29 with the exception of using the compositionobtained in step (20-3) instead of the composition obtained in step(5-2), and using 92.6 g of dibutyl tin dilaurate. As a result ofanalyzing the solution by ¹H- and ¹³C-NMR analysis, the solution wasfound to contain 99% by weight of4,4′-methylenebis(cyclohexyldiisocyanate). The yield based on4,4′-methylenebis(cyclohexylamine) was 77.5%. In addition, there were nosubstances observed to be adhered to the inside of the thin filmevaporation apparatus following the reaction.

Example 45 Production of 2,4-toluenediisocyanate UsingToluene-2,4-dicarbamic Acid Bis(3-methylbutyl) Ester/2,6-dimethylphenolComposition

325 g of a solution were recovered from line 67 by carrying out the samemethod as Example 29 with the exception of using the compositionobtained in step (21-3) instead of the composition obtained in step(5-2), and using 63.6 g of dibutyl tin dilaurate. As a result ofanalyzing the solution by ¹H- and ¹³C-NMR analysis, the solution wasfound to contain 99% by weight of 2,4-toluenediisocyanate. The yieldbased on 2,4-toluenediamine was 89.1%. In addition, there were nosubstances observed to be adhered to the inside of the thin filmevaporation apparatus following the reaction.

Example 46 Production of 2,4-toluenediisocyanate UsingToluene-2,4-dicarbamic Acid Dimethyl Ester/2,4-bis(α,α-dimethylbenzyl)Phenol Composition Step (46-1): Production of Toluene-2,4-dicarbamicAcid Bis(2,4-bis(α,α-dimethylbenzyl)phenyl) Ester by Transesterification

A transesterification reaction was carried out in a reaction apparatusas shown in FIG. 3.

5433 g of a reaction liquid were recovered from line 44 by carrying outthe same method as step (37-1) of Example 37 with the exception of usingthe composition obtained in step (22-2) of Example 22 instead of thecomposition obtained in step (13-3) of Example 13, and using 46.3 g ofdibutyl tin dilaurate.

As a result of analyzing the extracted reaction liquid by liquidchromatography, the reaction liquid was found to contain 14.9% by weightof toluene-2,4-dicarbamic acid bis(2,4-bis(α,α-dimethylbenzyl)phenyl)ester. In addition, as a result of analyzing the solution recovered fromline 47 by ¹H- and ¹³C-NMR analysis, the solution was found to contain98% by weight of methanol.

Step (46-2): Production of 2,4-toluenediisocyanate by ThermalDecomposition Toluene-2,4-dicarbamic AcidBis(2,4-bis(α,α-dimethylbenzyl)phenyl) Ester

319 g of a solution were recovered from line 75 by carrying out the samemethod as step (37-2) of Example 37 with the exception of using thesolution obtained in step (38-1) instead of the solution obtained instep (37-1). As a result of analyzing the solution by ¹H- and ¹³C-NMRanalysis, the solution was found to contain 99% by weight of2,4-toluenediisocyanate. The yield based on 2,4-toluenediamine was87.3%.

Example 47 Production of 4,4′-methylenebis(phenylisocyanate) UsingN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic Acid Bis(3-methylbutyl)Ester/2,4-di-tert-amylphenol Composition

469 g of a solution were recovered from line 67 by carrying out the samemethod as Example 29 with the exception of using the compositionobtained in step (23-3) instead of the composition obtained in step(5-2), and using 63.0 g of dibutyl tin dilaurate. As a result ofanalyzing the solution by ¹H- and ¹³C-NMR analysis, the solution wasfound to contain 99% by weight of 4,4′-methylenebis(phenylisocyanate).The yield based on 4,4′-methylenedianiline was 89.3%. In addition, therewere no substances observed to be adhered to the inside of the thin filmevaporation apparatus following the reaction.

Example 48 Production 4,4′-methylenebis(phenylisocyanate) UsingN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic Acid DibutylEster/2,4,6-trimethylphenol Composition Step (48-1): Production ofN,N′-(4,4′-methanediyl-diphenyl)-biscarbamic AcidBis(2,4,6-trimethylphenyl) Ester by Transesterification

A transesterification reaction was carried out in a reaction apparatusas shown in FIG. 3.

2321 g of a reaction liquid were recovered from line 44 by carrying outthe same method as step (28-1) of Example 28 with the exception of usingthe composition obtained in step (24-3) of Example 24 instead of thecomposition obtained in step (4-3) of Example 4, and using 57.6 g ofdibutyl tin dilaurate. As a result of analyzing the extracted reactionliquid by liquid chromatography, the reaction liquid was found tocontain 39.0% by weight of N,N′-(4,4′-methanediyl-diphenyl)-biscarbamicacid bis(2,4,6-trimethylphenyl) ester. In addition, as a result ofanalyzing the solution recovered from line 27 by ¹H— and ¹³C-NMRanalysis, the solution was found to contain 98% by weight of 1-butanol.

Step (48-2): Production of 4,4′-methylenebis(phenylisocyanate) byThermal Decomposition of N,N′-(4,4′-methanediyl-diphenyl)-biscarbamicAcid Bis(2,4,6-triphenyl) Ester

420 g of a solution containing 99% by weight of 4,4′-methylenebis(phenylisocyanate) were recovered from line 32 by carrying out the samemethod as step (28-2) of Example 28 with the exception of using thesolution obtained in step (48-1) instead of the solution obtained instep (28-1). The yield based on 4,4′-methylenedianiline was 88.3%. Inaddition, there were no substances observed to be adhered to the insideof the thin film evaporation apparatus following the reaction.

Example 49

Production of hexamethylene diisocyanate was carried out in a reactionapparatus as shown in FIG. 6.

Step (49-1): N,N′-hexanediyl-bis-carbamic Acid Bis(3-methylbutyl) EsterProduction Step

A stirring tank 801 (internal volume: 30 L) was heated to 80° C.

Bis(3-methylbutyl)carbonate, produced using the same method as step(1-1) of Example 1 and preheated to 80° C., was transferred to thestirring tank 801 from a line 80 at the rate of 1820 g/hr with a line 82closed, and a mixed solution of hexamethylene diamine,3-methyl-1-butanol and sodium methoxide (28% methanol solution) (mixingratio: hexamethylene diamine 50 parts/3-methyl-1-butanol 50 parts/sodiummethoxide 4.2 parts) was simultaneously transferred from a line 81 atthe rate of 209 g/hr. After 5 hours, line 82 was opened with a line 83closed, and the solution was housed in a basic sulfonic acid ionexchange resin (Amberlyst-15, spherical, Rohm and Haas Co., USA)adjusted by removing the moisture and supplied to an ion exchange resincolumn 812 maintained at 80° C. by an external jacket to neutralize thesodium methoxide, followed by transferring to a tank 802 through a line84. Lines 82 and 83 were maintained at 80° C. to prevent precipitationof solids from the reaction liquid.

When the reaction liquid transferred to tank 802 was analyzed by liquidchromatography, the reaction liquid was found to contain 29.7% by weightof N,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester.

Step (49-2): Low Boiling Point Component Distillation Step

The reaction liquid produced in step (49-1) was transferred from tank802 to stirring tank 803 maintained at 80° C. through line 84 at therate of 130 g/hr. 2,4-Di-tert-amylphenol heated to 80° C. wassimultaneously added to stirring tank 803 from a line 85 at the rate of131 g/hr to obtain a homogeneous solution. The solution was transferredto a thin film distillation apparatus 804 (Kobelco Eco-Solutions Co.,Ltd., Japan, heat-conducting surface area of 0.2 m²) heated to 150° C.and set to an internal pressure of 0.1 kPa through a line 86 maintainedat 80° C. at the rate of 261 g/hr where a low boiling point componentcontained in the solution were distilled off. The low boiling pointcomponent that had been distilled off was extracted from the thin filmdistillation apparatus 803 from a line 87. On the other hand, a highboiling point component was extracted from the thin film distillationapparatus 803 via a line 88 maintained at 80° C., and transferred to atank 805 maintained at 80° C. Dibutyl tin dilaurate was added to tank805 from line 89 at the rate of 16.7 g/hr.

When the solution stored in the tank 605 was analyzed by liquidchromatography, the solution was found to contain 24.1% by weight ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester.

Step (49-3): Hexamethylene Diisocyanate Production Step by ThermalDecomposition of N,N′-hexanediyl-bis-carbamic Acid Bis(3-methylbutyl)Ester

The solution stored in tank 805 was supplied to a thin film distillationapparatus 806 (Kobelco Eco-Solutions Co., Ltd., Japan, heat-conductingsurface area of 0.1 m²) heated to 200° C. and set to an internalpressure of about 1.3 kPa via line 90 at the rate of 800 g/hr. A gaseouscomponent containing hexamethylene diisocyanate, 3-methyl-1-butanol and2,4-di-tert-amylphenol was extracted from a line 95 provided in theupper portion of the thin film distillation apparatus 806. The gaseouscomponent was introduced into a distillation column 807 to separate the3-methyl-1-butanol, and a portion of a high boiling point component wasreturned to thin film distillation apparatus 806 via a line 94 providedin the bottom of distillation column 807 after passing through a line93. A gaseous component containing hexamethylene diisocyanate and2,4-di-tert-amylphenol was extracted from a line 97 provided indistillation column 807 and introduced into a distillation column 810.The hexamethylene diisocyanate was separated in this distillation column810. After reacting for 12 hours, a solution was recovered from a line99 at the rate of about 88 g/hr, and as a result of analyzing by ¹H- and¹³C-NMR analysis, the solution was found to contain 99% by weight ofhexamethylene diisocyanate. The yield based on hexamethylene diamine was92%. In addition, there were no substances observed to be adhered to theinside of the thin film evaporation apparatus following the reaction.

Example 50 Step (50-1): Production of Bis(3-methylbutyl) Carbonate

688 g (3.0 mol) of di-n-butyl tin oxide (Sankyo Organic Chemicals Co.,Ltd., Japan) and 2222 g (25.0 mol) of 3-methyl-1-butanol (Kuraray Co.,Ltd., Japan) were placed in a 5000 mL volumetric pear-shaped flask. Theflask was connected to an evaporator (R-144, Shibata Co., Ltd., Japan)to which was connected an oil bath (OBH-24, Masuda Corp., Japan)equipped with a temperature controller, a vacuum pump (G-50A, ULVACInc., Japan) and a vacuum controller (VC-10S, Okano Seisakusho Co.,Ltd.). The purge valve outlet of this evaporator was connected to a linecontaining nitrogen gas flowing at normal pressure. After closing thepurge valve of the evaporator to reduce pressure inside the system, thepurge valve was opened gradually to allow nitrogen to flow into thesystem and return to normal pressure. The oil bath temperature was setto about 145° C., the flask was immersed in the oil bath and rotation ofthe evaporator was started. After heating for about 40 minutes in thepresence of atmospheric pressure nitrogen with the purge valve of theevaporator left open, distillation of 3-methyl-1-butanol containingwater began. After maintaining in this state for 7 hours, the purgevalve was closed, pressure inside the system was gradually reduced, andexcess 3-methyl-1-butanol was distilled with the pressure inside thesystem at 74 to 35 kPa. After the fraction no longer appeared, the flaskwas taken out of the oil bath. After allowing the flask to cool to thevicinity of room temperature (25° C.), the flask was taken out of theoil bath, the purge valve was opened gradually and the pressure insidethe system was returned to atmospheric pressure. 1290 g of reactionliquid were obtained in the flask. Based on the results of ¹¹⁹Sn-, ¹H-and ¹³C-NMR analyses, 1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy)distannoxane was confirmed to have been obtained at a yield of 99% basedon di-n-butyl tin oxide. The same procedure was then repeated 12 timesto obtain a total of 11368 g of1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane.

Bis(3-methylbutyl)carbonate was produced in a continuous productionapparatus like that shown in FIG. 7.1,1,3,3-Tetrabutyl-1,3-bis(3-methylbutyloxy) distannoxane produced inthe manner described above was supplied at the rate of 4388 g/hr from atransfer line A4 into a column-type reaction vessel A102 packed withMetal Gauze CY Packing (Sulzer Chemtech Ltd., Switzerland) and having aninner diameter of 151 mm and effective length of 5040 mm. On the otherhand, 3-methyl-1-butanol was supplied to a distillation column A101 froma tank A100 by line A1, and the 3-methyl-1-butanol purified indistillation column A101 was supplied at the rate of 14953 g/hr tocolumn-type reaction vessel A102 from a line A2. The liquid temperatureinside reaction vessel A102 was controlled to 160° C. by a heater and areboiler A112, and the pressure was adjusted to about 120 kPa-G with apressure control valve. The residence time in the reaction vessel wasabout 17 minutes. 3-Methyl-1-butanol containing water at the rate of15037 g/hr from the top of the reaction vessel via a transfer line A6,and 3-methyl-1-butanol at the rate of 825 g/hr via feed line A1, werepumped to distillation column A101 packed with Metal Gauze CY Packingand provided with a reboiler A111 and a condenser A121 to carry outdistillative purification. In the top of distillation column A101, afraction containing a high concentration of water was condensed bycondenser A121 and recovered from a recovery line A3. Purified3-methyl-1-butanol was pumped to column-type reaction vessel A102 viatransfer line A2 located in the lower portion of distillation columnA101. An alkyl tin alkoxide catalyst composition containingdi-n-butyl-bis(3-methylbutyloxy) tin and1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane wasobtained from the lower portion of column-type reaction vessel A102, andsupplied to a thin film evaporation apparatus A103 (KobelcoEco-Solutions Co., Ltd., Japan) via a transfer line A5. The3-methyl-1-butanol was distilled off in thin film evaporation apparatusA103 and returned to column-type reaction vessel A102 via a condenserA123, a transfer line A8 and transfer line A4. The alkyl tin alkoxidecatalyst composition was pumped from the lower portion of thin filmevaporation apparatus A103 via a transfer line A7 and supplied to anautoclave A104 while adjusting the flow rate ofdi-n-butyl-bis(3-methylbutyloxy) tin and1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane to about5130 g/hr. Carbon dioxide was supplied to the autoclave by a transferline A9 at the rate of 973 g/hr, and the pressure inside the autoclavewas maintained at 4 MPa-G. The temperature inside the autoclave was setto 120° C., the residence time was adjusted to about 4 hours, and areaction between the carbon dioxide and the alkyl tin alkoxide catalystcomposition was carried out to obtain a reaction liquid containingbis(3-methylbutyl)carbonate. This reaction liquid was transferred to adecarbonization tank A105 via a transfer line A10 and a control valve toremove residual carbon dioxide, and the carbon dioxide was recoveredfrom a transfer line A11. Subsequently, the reaction liquid wastransferred to a thin film evaporation apparatus (Kobelco Eco-SolutionsCo., Ltd., Japan) A106 set to about 142° C. and about 0.5 kPa via atransfer line A12 and supplied while adjusting the flow rate of1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane to about4388 g/hr to obtain a fraction containing bis(3-methylbutyl)carbonate.On the other hand, the evaporation residue was circulated to column-typereaction vessel A102 via transfer line A13 and transfer line A4 whileadjusting the flow rate of 1,1,3,3-tetrabutyl-1,3-bis(3-methylbutyloxy)distannoxane to about 4388 g/hr. The fraction containingbis(3-methylbutyl)carbonate was supplied to a distillation column A107packed with Metal Gauze CY packing and equipped with a reboiler A117 anda condenser A127 via a condenser A126 and a transfer line A14 at therate of 959 g/hr followed by distillative purification to obtain 99 wt %bis(3-methylbutyl)carbonate from a recovery line A15 at the rate of 944g/hr. The bis(3-methylbutyl)carbonate was stored in a tank A108. Whenthe alkyl tin alkoxide catalyst composition of a transfer line A13 wasanalyzed by ¹¹⁹Sn-, ¹H- and ¹³C-NMR analysis, it was found to contain1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane but notcontain di-n-butyl-bis(3-methylbutyloxy) tin. After carrying out theabove-mentioned continuous operation for about 240 hours, alkyl tinalkoxide catalyst composition was extracted from an extraction line A16at the rate of 20 g/hr, while1,1,3,3-tetra-n-butyl-1,3-bis(3-methylbutyloxy) distannoxane producedaccording to the above process was supplied from a feed line A17 at therate of 20 g/hr.

Step (50-2): N,N′-hexanediyl-bis-carbamic Acid Bis(3-methylbutyl) EsterProduction Step

A stirring tank A110 was heated to 80° C. Bis(3-methylbutyl)carbonatewas transferred to the stirring tank A110 from a tank A108 by a line A21at the rate of 1214 g/hr with a line A22 closed, and a mixed solution ofhexamethylene diamine, 3-methyl-1-butanol and sodium methoxide (28%methanol solution) (mixing ratio:hexamethylene diamine 50parts/3-methyl-1-butanol 50 parts/sodium methoxide 0.42 parts) wassimultaneously transferred from a line 61 at the rate of 234 g/hr. After4 hours, line A22 was opened with a line A23 closed, and transfer of thereaction liquid was started to a stirring tank A111 maintained at 80° C.at the rate of 1448 g/hr. Line A22 was maintained at 80° C. to preventprecipitation of solids from the solution. At the same time,2,4-di-tert-amylphenol was transferred from a tank A109 to stirring tankA111 through a line A25 at the rate of 2225 g/hr to obtain a homogeneoussolution in stirring tank A111. The solution was then stored in astirring tank A112 maintained at a temperature of 80° C. via line A23.

When the mixed liquid transferred to tank A112 was analyzed by liquidchromatography, the mixed liquid was found to contain 9.2% by weight ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester.

Step (50-3): Low Boiling Point Component Distillation Step

A thin film distillation apparatus A113 (Kobelco Eco-Solutions Co.,Ltd., Japan, heat-conducting surface area of 0.2 m²) was heated to 150°C. and set to an internal pressure of about 0.1 kPa.

The solution stored in tank A112 was transferred to thin filmdistillation apparatus A113 by line A24 maintained at 80° C. at the rateof 3673 g/hr where a low boiling point component contained in thesolution was distilled off. The low boiling point component which wasdistilled off was extracted from the thin film distillation apparatusA113 through a line A27. The extracted low boiling point component wasintroduced into a distillation column A118 to carry out distillativeseparation, and 3-methyl-1-butanol was recovered from a line A30 andstored in a tank A100. On the other hand, a high boiling point componentwas extracted from the thin film distillation apparatus A113 by a lineA26 maintained at 150° C., and transferred to a stirring tank A114maintained at 80° C. Dibutyl tin dilaurate was simultaneouslytransferred to stirring tank A114 from a line 67 at the rate of 29 g/hrto obtain a homogeneous solution.

The mixed liquid prepared in the stirring tank A114 was transferred to atank A115 by a line A32 with a line A33 closed and stored in tank A115.When the solution stored in tank A115 was analyzed by liquidchromatography, the solution was found to contain 13.4% by weight ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester.

Step (50-4): N,N′-hexanediyl-bis-carbamic AcidBis(2,4-di-tert-amylphenyl) Ester Production Step by Transesterification

A thin film distillation apparatus A116 (Kobelco Eco-Solutions Co.,Ltd., Japan, heat-conducting surface area of 0.2 m²) was heated to 240°C.

A transesterification reaction was carried out by transferring a mixedliquid of N,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester,2,4-di-tert-amylphenol and dibutyl tin dilaurate stored in tank A115 tothin film distillation apparatus A116 via a line A32 at the rate of 2436g/hr with a line A36 closed. A mixed gas containing 3-methyl-1-butanoland 2,4-di-tert-amylphenol was extracted from a line A37 provided in theupper portion of the thin film distillation apparatus A116, and suppliedto a distillation column A119. The 3-methyl-1-butanol and2,4-di-tert-amylphenol were separated in the distillation column A119,and the 3-methyl-1-butanol was extracted by line A39 and stored in tankA100 via line A40. On the other hand, the 2,4-di-tert-amylphenol wasreturned to the upper portion of thin film distillation apparatus A116via a line A38 provided in the bottom of distillation column A119. Areaction liquid was extracted from a line A34 provided in the bottom ofthe thin film distillation apparatus A116, and supplied to thin filmdistillation apparatus A116 via a line A35. When theN,N′-hexanediyl-bis-carbamic acid bis(2,4-di-tert-amylphenyl) ester inthe reaction liquid extracted from line A35 reached 25.2% by weight,line A36 was opened with line A41 closed and the reaction liquid wastransferred to a tank A121.

Step (50-5): Hexamethylene Diisocyanate Production Step by ThermalDecomposition of N,N′-hexanediyl-bis-carbamic AcidBis(2,4-di-tert-amylphenyl) Ester

The solution stored in tank A121 was supplied to a thin filmdistillation apparatus A122 (Kobelco Eco-Solutions Co., Ltd., Japan,heat-conducting surface area of 0.1 m²) heated to 200° C. and set to aninternal pressure of about 1.3 kPa via line A41 at the rate of 2306g/hr. A gaseous component containing hexamethylene diisocyanate wasextracted from a line A43 provided in the upper portion of the thin filmdistillation apparatus A122 and supplied to distillation column A123.Distillative separation was carried out in distillation column A123 andhexamethylene diisocyanate was recovered from line A45 at the rate of447 g/hr.

A high boiling point component separated with distillation column A123was extracted from line A47 and introduced into a distillation columnA126 via a line A48. 2,4-di-tert-amylphenol was separated from the highboiling point component in the distillation column A126 and transferredto tank A109 by line A49.

Although the above series of steps were carried out to recover 643 kg ofhexamethylene diisocyanate, there were no substances observed to beadhered to the inside of the thin film distillation apparatus followingthe reaction.

Comparative Example 1 Step (A-1): Production of Bis(3-methylbutyl)Carbonate

Bis(3-methylbutyl)carbonate was produced using the same method as step(1-1) of Example 1.

Step (A-2): Production of N,N′-hexanediyl-bis-carbamic AcidBis(3-methylbutyl) Ester

A solution containing 37.7% by weight of N,N-hexanediyl-bis-carbamicacid bis(3-methylbutyl)ester was obtained by carrying out the samemethod as step (1-2) of Example 1 with the exception of using 1537 g(7.6 mol) of bis(3-methylbutyl) carbonate obtained in step (A-1), using232 g (2.0 mol) of hexamethylene diamine, and using 19.3 g of sodiummethoxide (25% methanol solution).

Step (A-3): Distillation of Low Boiling Point Component

The solution obtained in step (A-2) was placed in a 10 L volumetricflask equipped with a three-way valve, condenser, distillate collectorand thermometer followed by replacing the inside of the flask withnitrogen in a vacuum. The flask was immersed in an oil bath heated to130° C. Distillation was carried out while gradually reducing thepressure within the apparatus to a final pressure within the apparatusof 0.13 kPa. 1078 g of a distillate were obtained. As a result ofanalyzing by gas chromatography, the distillate was found to be asolution containing 68.1% by weight of bis(3-methylbutyl)carbonate and31.5% by weight of 3-methyl-1-butanol. As a result of analyzing byliquid chromatography, the distillation residue obtained in the flaskwas found to contain 59.8% by weight of N,N′-hexanediyl-bis-carbamicacid bis(3-methylbutyl)ester, and the yield ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester based onhexamethylene diamine was 60.3%. The distillation residue was a liquidat 160° C. After maintaining at 160° C. for 1 day, the concentration ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester in thedistillation residue was 32.2% by weight.

Comparative Example 2 Step (B-1): Production ofN,N′-hexanediyl-bis-carbamic Acid Dimethyl Ester

A solution containing 34.1% by weight of N,N-hexanediyl-bis-carbamicacid dimethyl ester was obtained by carrying out the same method as step(1-2) of Example 1 with the exception of using 1625 g (18.0 mol) ofdimethyl carbonate instead of bis(3-methylbutyl)carbonate, using 349 g(3.0 mol) of hexamethylene diamine, and using 28.9 g of sodium methoxide(25% methanol solution).

Step (B-2): Distillation of Low Boiling Point Component

3972 g of a distillate were obtained by carrying out the same method asstep (1-3) of Example 1 with the exception of using the solutionobtained in step (B-1) and 2702 g of toluene (Wako Pure ChemicalIndustries, Ltd., Japan) instead of 2,4-di-tert-amylphenol. As a resultof analyzing by gas chromatography, the distillate was found to contain27.5% by weight of dimethyl carbonate, 4.7% by weight of methanol and67.7% by weight of toluene. As a result of analyzing by liquidchromatography, the distillation residue obtained in the flask was foundto contain 67.3% by weight of N,N′-hexanediyl-bis-carbamic acid dimethylester, and the yield of N,N′-hexanediyl-bis-carbamic acid dimethyl esterbased on hexamethylene diamine was 70.5%. The distillation residue was aliquid at 50° C. After maintaining at 50° C. for 10 days, theconcentration of N,N′-hexanediyl-bis-carbamic acidbis(3-methylbutyl)ester in the distillation residue was 31.6% by weight.

Comparative Example 3 Step (C-1): Production of Dibutyl Carbonate

Dibutyl carbonate was produced using the same method as step (7-1) ofExample 7.

Step (C-2): Production of N,N′-hexanediyl-bis-carbamic Acid DibutylEster

A solution containing 27.4% by weight of N,N-hexanediyl-bis-carbamicacid dibutyl ester was obtained by carrying out the same method as step(1-2) of Example 1 with the exception of using 2324 g (13.3 mol) ofdibutyl carbonate produced in step (C-1) instead ofbis(3-methylbutyl)carbonate, using 267 g (2.3 mol) of hexamethylenediamine, and using 13.3 g of sodium methoxide (25% methanol solution).

Step (C-3): Preparation of Composition

1901 g of a distillate were obtained by carrying out the same method asstep (1-3) of Example 1 with the exception of using the solutionobtained in step (C-1) and 2850 g of benzylbutyl phthalic acid (WakoPure Chemical Industries, Ltd., Japan) instead of2,4-di-tert-amylphenol. As a result of analyzing by gas chromatography,the distillate was found to contain 78.4% by weight of dibutyl carbonateand 16.8% by weight of 1-butanol. In addition, as a result of analyzingby liquid chromatography, the distillation residue obtained in the flaskwas found to contain 14.9% by weight of N,N′-hexanediyl-bis-carbamicacid dibutyl ester, and the yield of N,N′-hexanediyl-bis-carbamic aciddimethyl ester based on hexamethylene diamine was 71.3%. Thedistillation residue was a liquid at 70° C. After maintaining at 70° C.for 1 day, the concentration of N,N′-hexanediyl-bis-carbamic aciddibutyl ester in the distillation residue was 8.6% by weight.

Reference Example 4 Step (D-1): Production of Bis(3-methylbutyl)Carbonate

Bis(3-methylbutyl)carbonate was produced using the same method as step(1-1) of Example 1.

Step (D-2): Production of N,N′-hexanediyl-bis-carbamic AcidBis(3-methylbutyl) Ester

A solution containing 29.4% by weight of N,N-hexanediyl-bis-carbamicacid bis(3-methylbutyl)ester was obtained by carrying out the samemethod as step (1-2) of Example 1 with the exception of using 1922 g(9.5 mol) of bis(3-methylbutyl) carbonate obtained in step (D-1), using221 g (1.9 mol) of hexamethylene diamine, and using 18.3 g of sodiummethoxide (25% methanol solution).

Step (D-3): Preparation of Composition

4190 g of a distillate were obtained by carrying out the same method asstep (1-3) of Example 1 with the exception of using the solutionobtained in step (D-2) and 3117 g of 2,6-dimethylphenol instead of2,4-di-tert-amylphenol. As a result of analyzing by gas chromatography,the distillate was found to contain 27.8% by weight ofbis(3-methylbutyl)carbonate, 8.1% by weight of 3-methyl-1-butanol and64.4% by weight of 2,6-dimethylphenol. In addition, as a result ofanalyzing by liquid chromatography, the distillation residue obtained inthe flask was found to contain 80.7% by weight ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester, and the yieldof N,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester based onhexamethylene diamine was 85.1%. The distillation residue was a liquidat 150° C. After maintaining at 150° C. for 1 day, the concentration ofN,N′-hexanediyl-bis-carbamic acid bis(3-methylbutyl)ester in thedistillation residue was 42.1% by weight.

INDUSTRIAL APPLICABILITY

The composition according to the present invention is able to inhibit athermal denaturation reaction of carbamic acid ester. In addition, sinceisocyanate production process using this composition enables isocyanatesto be efficiently produced without using highly toxic phosgene, thecomposition according to the present invention and the isocyanateproduction process using this composition are highly useful industriallyand have high commercial value.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 illustrates a schematic drawing showing a continuous productionapparatus for producing carbonic acid ester used in an embodiment of thepresent invention;

FIG. 2 illustrates a schematic drawing showing an isocyanate productionapparatus used in an embodiment of the present invention;

FIG. 3 illustrates a schematic drawing showing a transesterificationreaction apparatus used in an embodiment of the present invention;

FIG. 4 illustrates a schematic drawing showing an isocyanate productionapparatus used in an embodiment of the present invention;

FIG. 5 illustrates a schematic drawing showing an isocyanate productionapparatus used in an embodiment of the present invention;

FIG. 6 illustrates a schematic drawing showing a continuous isocyanateproduction apparatus used in an embodiment of the present invention; and

FIG. 7 illustrates a schematic drawing showing a continuous isocyanateproduction apparatus used in an embodiment of the present invention.

BRIEF DESCRIPTION OF REFERENCE NUMERALS In FIG. 1

-   101, 107: distillation column, 102: column-type reaction vessel,    103, 106: thin film distillation apparatus, 104: autoclave, 105:    decarbonization tank, 111, 112, 117: reboiler, 121, 123, 126, 127:    condenser, 1, 9: feed line, 2, 4, 5, 6, 7, 8, 10, 11, 12, 13, 14:    transfer line, 3, 15: recovery line, 16: extraction line, 17: feed    line,

In FIG. 2

-   201: tank, 202: thin film distillation apparatus, 203, 204:    distillation column, 205, 207: condenser, 206, 208: reboiler, 21,    22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33: transfer line,

In FIG. 3

-   401: tank, 402: thin film distillation apparatus, 403: distillation    column, 404: condenser, 41, 42, 43, 44, 45, 46, 47, 48, 49: transfer    line

In FIG. 4

-   501: tank, 502: thin film distillation apparatus, 503, 504, 505:    distillation column, 507, 509, 511: condenser, 506, 508, 510:    reboiler, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64,    65, 66, 67, 68: transfer line

In FIG. 5

-   701: tank, 702: thin film distillation apparatus, 703: distillation    column, 704: reboiler, 705: condenser, 71, 72, 73, 74, 75, 76, 77,    78, 79: transfer line

In FIG. 6

-   801, 803: stirring tank, 812: ion exchange resin column, 802, 805:    tank, 804, 806: thin film distillation apparatus, 807, 810:    distillation column, 808, 812: condenser, 809, 811: reboiler, 80,    81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94 95, 96, 97,    98, 99, 100, 101: transfer line

In FIG. 7

-   A100, A108, A019, A112, A115, A121: tank, A101, A107, A118, A119,    A123, A126: distillation column, A102: column-type reaction vessel,    A103, A016, A113, A116, A122: thin film distillation apparatus,    A104: autoclave, A105: decarbonization tank, A110, A111, A114,    stirring tank, A129: ion exchange resin column, A132, A133, A136,    A130, A125, A127: reboiler, A131, A137, A134, A135, A117, A120,    A124, A128: condenser, A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11,    A12, A13, A14, A15, A16, A17, A20, A21, A22, A23, A24, A25, A26,    A27, A28, A29, A30, A31, A32, A33, A34, A35, A36, A37, A38, A39,    A40, A41, A42, A43, A44, A45, A46, A47, A48, A49, A50, A51: transfer    line

1. A process for producing an isocyanate using a composition containinga carbamic acid ester and an aromatic hydroxy compound, the processcomprising the step of transferring the composition to a reaction vesselin which a thermal decomposition reaction of the carbamic acid esteroccurs, wherein when number of mole of an ester group constituting thecarbamic acid ester is defined as A, and number of mole of the aromatichydroxy compound is defined as B, then a ratio of B to A is within arange of from 0.1 to 50, a melting point of the carbamic acid ester is200° C. or lower, and the aromatic hydroxy compound has a melting pointof 190° C. or lower and is an aromatic hydroxy compound which isrepresented by the following formula (1), and which has at least onesubstituent R¹:

(wherein ring A represents a single or multiple aromatic hydrocarbonring which may have a substituent, and which have 6 to 20 carbon atoms,and R¹ represents an aliphatic group having 1 to 20 carbon atoms, analiphatic alkoxy group having 1 to 20 carbon atoms, an aryl group having6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, anaralkyl group having 7 to 20 carbon atoms or an aralkyloxy group having7 to 20 carbon atoms, the above groups containing an atom selected fromthe group consisting of carbon, oxygen and nitrogen atoms, and R¹ maybond with A to form a ring structure).
 2. The process according to claim1, wherein isocyanate is produced by a process comprising the followingsteps (1), (3), (4) and (5), or a process comprising the following steps(2), (3), (4) and (5): step (1): reacting an amine compound and thecarbonic acid ester so as to obtain a mixture containing a carbamic acidester, an alcohol and a carbonic acid ester; step (2): reacting an aminecompound, an urea and an alcohol so as to obtain a mixture containing acarbamic acid ester, an alcohol and a urea compound; step (3):separating the alcohol and the carbonic acid ester or the urea containedin the mixture by using the mixture of step (1) or step (2) and thearomatic hydroxy compound so as to obtain a composition containing thecarbamic acid ester and the aromatic hydroxy compound; step (4):transferring the composition obtained in step (3) in a liquid state to areaction vessel in which step (5) is carried out; and step (5):producing the isocyanate using the composition transferred in step (4).3. The process according to claim 2, wherein a normal boiling point ofthe aromatic hydroxy compound is higher than a normal boiling point of acompound represented by ROH having a structure in which a hydrogen atomis added to RO constituting the ester group of the carbamic acid ester(wherein R represents an alkyl group and O represents an oxygen atom).4. The process according to claim 3, wherein a normal boiling point ofthe aromatic hydroxy compound is higher than a normal boiling point of acompound represented by ROCOOR having a structure in which an RO groupconstituting the ester group of the carbamic acid ester (wherein Rrepresents an alkyl group and O represents an oxygen atom) is bondedthrough a carbonyl group.
 5. The process according to claim 4, whereinthe step (3) is a step in which the composition containing the carbamicacid ester and the aromatic hydroxy compound is obtained from a mixtureof the mixture of the step (1) or the step (2) and the aromatic hydroxycompound by separating the alcohol and the carbonic acid ester or theurea.
 6. The process according to claim 5, wherein the step (3) is astep carried out in a distillation column, in which the compositioncontaining the carbamic acid ester and the aromatic hydroxy compound isobtained from a bottom of the distillation column by supplying themixture of the step (1) or the step (2) to the distillation column in aform of a mixture with the aromatic hydroxy compound, and recovering thealcohol and the carbonic acid ester or the urea from a top of thecolumn.
 7. The process according to claim 4, wherein the step (3) is astep in which a mixture obtained by separating all or a portion of thealcohol and/or a portion of the carbonic acid ester or the urea from themixture of the step (1) or the step (2) is mixed with the aromatichydroxy compound to obtain a mixture, and the carbonic acid ester or theurea is separated from the mixture.
 8. The process according to claim 7,wherein the step (3) is a step carried out in a distillation column, andfurther comprises the following steps (3-1) and (3-2): step (3-1):supplying the mixture of the step (1) or the step (2) to thedistillation column, an alcohol and/or a carbonic acid ester or an ureabeing recovered from a top of the column, and a mixture containing thecarbamic acid ester, the alcohol and/or the carbonic acid ester or theurea being recovered from a bottom of the column; and step (3-2):supplying the mixture of the step (3-1) to the distillation column in aform of a mixture with the aromatic hydroxy compound, the alcohol and/orthe carbonic acid ester or the urea being recovered from the top of thecolumn, and the composition containing the carbamic acid ester and thearomatic hydroxy compound being recovered from the bottom of the column.9. The process according to claim 2, further comprising a step in whichthe carbonic acid ester or the urea separated in the step (3) is reusedas the carbonic acid ester of the step (1) or the urea of the step (2).10. The process according to claim 2, wherein the step (4) is carriedout at 180° C. or lower.
 11. The process according to claim 2, whereinthe step (5) is a step in which the carbamic acid ester contained in thecomposition of the step (4) is subjected to a thermal decompositionreaction, and in which a low boiling point component formed by thethermal decomposition reaction is recovered as a gaseous component fromthe reaction vessel in which the thermal decomposition reaction occurs,and all or a portion of the mixture containing the carbamic acid esterand/or the aromatic hydroxy compound is recovered from the bottom of thereaction vessel.
 12. The process according to claim 11, wherein the lowboiling point component is an alcohol derived from the carbamic acidester.
 13. The process according to claim 2, wherein the step (5) is astep in which the composition of the step (4) is heated, the carbamicacid ester and the aromatic hydroxy compound which are contained in thecomposition are reacted to obtain an aryl carbamate having a groupderived from the aromatic hydroxy compound, and the aryl carbamate issubjected to a thermal decomposition reaction so as to produce anisocyanate.
 14. The process according to claim 13, wherein the step (5)comprises the following step (5-1) and step (5-2): step (5-1): reactingthe carbamic acid ester and aromatic hydroxy compound which arecontained in the composition of the step (4), a low boiling pointcomponent formed being recovered in a form of a gaseous component, and areaction liquid containing the aryl carbamate and the aromatic hydroxycompound being removed from the bottom of the reaction vessel in whichthe reaction occurs; and step (5-2): supplying the reaction liquid ofthe step (5-1) to a reaction vessel in which a thermal decompositionreaction occurs, the aryl carbamate being subjected to a thermaldecomposition reaction, at least one of either an isocyanate or anaromatic hydroxy compound which are formed being recovered in a form ofa gaseous component, and all or a portion of a mixture containing theisocyanate and/or the aromatic hydroxy compound and/or the arylcarbamate not recovered in a form of a gaseous component being recoveredfrom the bottom of the reaction vessel.
 15. The process according toclaim 14, wherein the low boiling point component of the step (5-1) isan alcohol derived from the carbamic acid ester.
 16. The processaccording to claim 11 or 14, wherein the aromatic hydroxy compound isrecovered from the mixture according to claim 11 recovered from thebottom of the reaction vessel and containing the carbamic acid esterand/or the aromatic hydroxy compound, or the reaction liquid of the step(5-1) according to claim 14, the mixture recovered from the bottom ofthe reaction vessel and/or the compound recovered in the form of agaseous component in step the (5-2) according to claim 14, and thearomatic hydroxy compound is reused as the aromatic hydroxy compound ofthe step (3).
 17. The process according to claim 2, wherein the alcoholseparated in the step (3) according to claim 2 and/or the alcoholaccording to claim 10 and/or claim 13, is used as all or a portion ofthe alcohol in the step (2) according to claim
 2. 18. The processaccording to claim 4, wherein a molecular weight of the aromatic hydroxycompound is within a range of from 120 to
 370. 19. The process accordingto claim 18, wherein the aromatic hydroxy compound is a compound havingone hydroxyl group directly bonded to an aromatic hydrocarbon ringconstituting the aromatic hydroxy compound.
 20. (canceled)
 21. Theprocess according to claim 1, wherein the aromatic hydroxy compound hasa structure in which ring A contains at least one structure selectedfrom the group consisting of a benzene ring, a naphthalene ring and ananthracene ring.
 22. The process according to claim 21, wherein thearomatic hydroxy compound is a compound represented by the followingformula (2):

(wherein, each of R², R³, R⁴, R⁵ and R⁶ independently represents ahydrogen atom, or an aliphatic group having 1 to 20 carbon atoms, analiphatic alkoxy group having 1 to 20 carbon atoms, an aryl group having6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, anaralkyl group having 7 to 20 carbon atoms or an aralkyloxy group having7 to 20 carbon atoms, the above groups containing an atom selected fromthe group consisting of carbon, oxygen and nitrogen atoms, and at leastone of R², R³, R⁴, R⁵ and R⁶ is not a hydrogen atom).
 23. The processaccording to claim 22, wherein the aromatic hydroxy compound is acompound represented by the formula (2) in which R² is not a hydrogenatom.
 24. The process according to claim 23, wherein the aromatichydroxy compound is a compound represented by the formula (2) in which atotal number of carbon atoms constituting R² and R⁶ is from 2 to
 20. 25.The process according to claim 2, wherein the amine compound of the step(1) is a polyamine compound.
 26. The process according to claim 25,wherein the amine compound is a compound represented by the followingformula (3):

(wherein R⁷ represents a group which is selected from the groupconsisting of an aliphatic group having 1 to 20 carbon atoms and anaromatic group having 6 to 20 carbon atoms, the aliphatic group and thearomatic group contain an atom selected from carbon and oxygen atoms,and have a valence equal to n, and n represents an integer of 2 to 10).27. The process according to claim 26, wherein the polyamine compound isa diamine compound in which n in the formula (3) is
 2. 28. The processaccording to claim 27, wherein the diamine compound is a compound inwhich R⁷ in the formula (3) is an aliphatic group which has 1 to 20carbon atoms, and which contains an atoms selected from carbon andoxygen atoms.
 29. The process according to claim 28, wherein the diaminecompound is at least one compound selected from the group consisting ofcompounds represented by the following formulas (4), (5) and (6):


30. The process according to claim 2, wherein the carbonic acid ester isa compound represented by the following formula (7):

(wherein R⁸ represents a linear or branched alkyl group having 1 to 8carbon atoms).
 31. The process according to claim 30, wherein thecarbonic acid ester is produced by a process comprising the followingstep (A) and step (B): step (A): reacting an organic tin compound havinga tin-oxygen-carbon bond and carbon dioxide so as to obtain a reactionmixture containing the carbonic acid ester; and step (B): separating thecarbonic acid ester from the reaction mixture as well as obtaining adistillation residue.
 32. The process according to claim 31, furthercomprising the following step (C) and step (D) in addition to the step(A) and the step (B) according to claim 31: step (C): reacting thedistillation residue obtained in step (B) with alcohol so as to form anorganic tin compound having a tin-oxygen-carbon bond and a water,followed by removing the water from a reaction system; and step (D):reusing the organic tin compound having the tin-oxygen-carbon bondobtained in the step (C) as the organic tin compound having atin-oxygen-carbon bond of step (A).
 33. The process according to claim32, wherein the alcohol separated in the step (3) according to claim 2and/or the alcohol according to claim 10 and/or claim 13 is used as allor a portion of the alcohol in the step (C) according to claim
 32. 34.The process according to claim 2, wherein the alcohol of the step (1) isan alcohol having an alkyl group derived from the carbonic acid ester.35. The process according to claim 2, wherein the reaction between theamine compound and the carbonic acid ester in the step (1) is carriedout in the presence of a metal alkoxide compound.
 36. The processaccording to claim 35, wherein the metal alkoxide compound is analkoxide compound of an alkaline metal or an alkaline earth metal. 37.The process according to claim 36, wherein an alkyl group constitutingthe carbonic acid ester is identical to an alkyl group constituting themetal alkoxide compound.
 38. The process according to claim 2, whereinthe alcohol of the step (2) is a compound represented by the followingformula (8):R⁹—OH  (8) (wherein R⁹ represents a linear or branched alkyl grouphaving 1 to 10 carbon atoms).
 39. The process according to claim 2,wherein the carbamic acid ester is a polycarbamic acid ester.
 40. Theprocess according to claim 39, wherein the polycarbamic acid ester is acompound represented by the following formula (9):

(wherein R⁷ has the same meaning as defined above, R¹¹ represents analiphatic group or an aromatic group which has 1 to 10 carbon atoms, andwhich contains an atom selected from carbon and oxygen atoms, and nrepresents an integer of 2 to 10).
 41. The process according to claim40, wherein the polycarbamic acid ester is a compound represented by theformula (9) in which n is
 2. 42. The process according to claim 41,wherein the polycarbamic acid ester is a compound represented by theformula (9) in which R¹¹ is an aliphatic group which has 1 to 10 carbonatoms, and which contains an atom selected from carbon and oxygen atoms.43. The process according to claim 42, wherein the polycarbamic acidester is a compound represented by the formula (9) in which R⁷ is agroup selected from the group consisting of an alkyl group having 1 to20 carbon atoms and a cycloalkyl group having 5 to 20 carbon atoms. 44.The process according to claim 43, wherein the polycarbamic acid esteris at least one of compound selected from the group consisting ofcompounds represented by the following formulas (10), (11) and (12):

(wherein R¹¹ has the same meaning as defined above).
 45. A compositionfor transfer and storage of a carbamic acid ester comprising: a carbamicacid ester; and an aromatic hydroxy compound, wherein when number ofmole of an ester group constituting the carbamic acid ester is definedas A, and number of mole of an aromatic hydroxy compound is defined asB, then a ratio of B to A is within a range of from 0.1 to 50, a meltingpoint of the carbamic acid ester is 200° C. or lower, and a meltingpoint of the aromatic hydroxy compound is 190° C. or lower.